锇、钌、铱杂环化合物的合成、表征及反应性研究

详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文

英文题名：Synthesis, Characterization and Reactivity of Osmacycles, Ruthenacycles and Iridacycles 作者：龚磊 论文级别：博士 学科专业名称：高分子化学与物理 中文关键词：金属杂环化合物 ; 金属杂IC化合物 ; 金属苯 ; 锇呋喃 ; [n+1]关环法 英文关键词：Metallacycles ; Intramolecular-coordination metallacycles ; Metallabenzenes ; Osmafuran ; [n+1] Cyclization reaction 学位年度：2008 导师：夏海平 学科代码：070305 学位授予单位：厦门大学 论文提交日期：2008-07-01

摘要

杂环化学是有机化学中最活跃的研究领域之一,它与生命科学、材料科学等学科均有着十分密切的联系。杂环化合物的研究不仅在理论上有着重要的指导意义,而且在实际应用方面也不断影响着人们的日常生活。随着其研究的快速发展,杂环化合物的杂原子已由O、S、N、P、Si等非金属元素拓展到过渡金属元素。过渡金属种类多、有d、f轨道、多价态、可引入不同官能配体,它们的引入使得杂环化学的分子设计空间得到极大的拓展。过渡金属杂环化合物特殊的分子结构、化学活性、物理性能及潜在的应用前景给化学的多个二级学科和生命与材料科学相关领域的发展带来全新的机遇和挑战。
     本论文将课题组[5+1]关环合成金属苯双季鏻盐的方法发展为简便的[n+1]关环法,并将该法应用到多类金属杂环化合物的合成中,制备了一系列结构新颖的锇、钌、铱杂五、六元环化合物。也对这些化合物进行了系统的表征,还初步研究了部分化合物的反应性:
     第一章为绪论,对过渡金属杂环化合物的研究现状、结构特点、合成方法以及潜在的催化性能进行了简单的评述。同时,结合本论文的核心内容,分别介绍了过渡金属杂芳香化合物和分子内配位过渡金属有机化合物(IC化合物)的研究进展。此外,对文章的主要设想与目的也进行了阐述。
     第二章主要研究基于[5+1]关环法的锇杂环化合物合成。本章分别以C_5有机配体HC≡CCH(OH)CH=CH_2和HC≡CC(CH_3),(OH)CH=CH_2与锇配合物OsCl_2(PPh_3)_3反应,利用PPh_3对配位炔烃的加成和末端烯烃或炔烃对金属配位的协同反应来完成[5+1]关环,从而发现了合成锇杂环配合物的简便、有效的新方法。首先,合成出两种具有反应活性的金属杂五元环IC配合物OsCl_2(PPh_3)_2(CH=C(PPh_3)CH(OH)CH=CH_2和OsCl_2(PPh_3)_2(CH=C(PPh_3)C(=CH_2)-CH=CH_2,并对它们进行了系统表征;进而,研究了这些活性五元配合物的反应性,合成出多种稳定的锇杂环配合物,其中包括锇苯、锇呋喃、含配位联烯的锇杂IC环化合化物、含锇卡宾的IC环化物、首例锇杂环戊二烯化合物等多元化的产物。
     第三章主要阐述从锇苯中间体合成锇杂环化合物的方法。探讨了锇苯中间体的反应性,合成出首例稳定的对一金属苯酚、含α,β-不饱和酮的锇杂环IC化合物,锇呋喃,锇杂环戊二烯化合物等化合物,并进行了系统表征和反应机理推测。
     第四章为金属苯反应性的初步研究。初步考察了本课题组两种代表性金属苯-锇苯和钌苯的三类反应:脱氯反应、与含氮多齿配体的反应、与醛/Lewis酸的金属苯开环反应,制备了多种金属有机配合物和有机化合物,其中包括两类结构新颖的非配位型双金属苯。
     第五章主要研究基于[4+1]关环法的铱杂环化合物合成。探索了18e配位饱和的铱氢配合物IrHCl(PPh_3)_3与三种类型的炔烃HC≡CCH(OH)C≡CH,C_6H_5C≡CH,C_6H_5CH(OH)C≡CH的反应。这些反应以[4+1]关环法为基础,涉及PPh_3对炔烃的加成、金属氢对炔烃的加成、碳氢活化等多种反应历程,合成了共轭桥联铱氧杂六元环二聚体(即含十个sp~2杂化碳桥联的铱二聚体)、铱茚配合物等结构新颖的铱杂五、六元环化合物。此外,还对共轭桥联铱氧杂六元环二聚体的热性能、电化学性能及反应性进行了研究。
     第六章总结了本论文研究工作的创新性,并对后续的工作进行了展望。
Heterocyclic chemistry is one of the most active research fields of organic chemistry, which has close connection with life science and material science. Research into heterocyclic compounds has important guiding significance in theory. And its application research also affect people's daily life greatly. A wide variety of new heterocyclic compounds, encompassing transition-metal elements as hetero atoms, is now available. Owing to the characteristic of transition-metal, the molecular design space of heterocyclic compounds has expanded significantly. Because of the special structures, chemical activities, physical properties and potential application prospects of transition-metal-containing metallacycles, there exist many new opportunities and challenges to further develop the related fields of chemistry, biology and material science.
     In this dissertation,convenient [n+1] cyclization reaction was described which was developed from [5+1] cyclization reaction synthesizing metallabenzenes by our group, and applied in the synthesis several novel 5- or 6-membered metallacycles containing osmium, ruthium and iridium. The reactivities of some complexes havealso been studied preliminarily in the research.
     The dissertation contains six chapters: (1) research progress in metallacycles; (2) synthesis of osmacycles based on [5+1] cyclization reaction; (3) synthesis of several osmacycles based on the reactivity of an osmabenzene intermediate complex; (4) preliminary studies on the reactivity of metallabenzenes; (5) synthesis of iridacycles based on [4+1] cyclization reaction; (6) Innovation and prospect.
     Chapter 1 reviews the research progress, structural characteristics, synthesis methods and potential catalytic properties of transition-metal-containing metallacycles. According to the main objective of this dissertation, the research progress of transition-metal-containing metallaromatic complexes and intramolecular-coordination metallacycles is also reviewed in this chapter. In addition, the research objectives of this dissertation are presented.
     Chapter 2 is mainly about synthesis of osmacycles based on [5+1] cyclization reaction.Two active five-membered intramolecular-coordination osmacycles O_SCl_2(PPh_3)_2(CH=C(PPh_3)CH(OH)CH=CH_2 and O_SCl_2(PPh_3)_2(CH=C(PPh_3)-C(=CH_2)CH=CH_2 were synthesized from the reactions of C_5 reagants (HC≡CCH(OH)CH=CH_2 or HC≡CC(CH_3)(OH)CH=CH_2) with an osmium complex O_SCl_2(PPh_3)_3.These cyclometallation process contained the addtion reactions of PPh_3 and the coordinations of the terminal alkyne or alkene groups. During the investigation of the reactivity of O_SCl_2(PPh_3)_2(CH=C(PPh_3)CH(OH)CH=CH_2 and O_SCl_2(PPh_3)_2(CH=C(PPh_3)C(=CH_2)CH=CH2, several stable osmacycles with novel structure, such as osmabenzenes, osmafurans, osmacycles containing intramolecular-coordinated allene, intramolecular-coordination osmacycles containing osmacarbene, an osmacyclopentadiene, were isolated during the investigation of the reactivity of O_SCl_2(PPh_3)_2(CH=C(PPh_3)CH(OH)CH=CH_2 and O_SCl_2(PPh_3)_2-(CH=C(PPh_3)C(=CH_2)CH=CH_2.In addition, some convenient and efficient methods to prepare these osmacycles were developed.
     In chapter 3, the studies on synthesis of osmacycles from an osmabenzene intermediate complex is discussed. The first p-osmaphenol,several osmacycles containing intramolecular-coordinatedα,β-unsaturated ketone, an osmafuran, an osmacyclopentadiene were synthesized and well characterized. And the plausible mechanisms for the formation of these complexes were also proposed in this chapter.
     Chapter 4 describes preliminary studies on the reactivity of metallabenzenes. Three kinds of reactions of the representative osmabenzene and ruthenabenzene synthesized by our group, including dechloride reactions, substitution reactions with polydentate nitrogen-containing ligands, and reactions with aldehydes/Lewis acids systems, were investigated. During the investigation, several organometallic complexes and organic compounds, including two none-coordinated bisruthenabenzenes, were obtained.
     Chapter 5 describes the synthesis of iridacycles based on [4+1] cyclization reaction. In this chapter, three different alkynes, HC≡CCH(OH)C≡CH,C_6H_5C≡CH and C_6H_5CH(OH)C≡CH,reacted respectively with 18e iridium hydride complex IrHCl(PPh_3)_3.These reactions were based on [4+1] cyclization reaction and involved the additions of PPh_3 to the alkyne groups, additions of indium hydride to the alkyne groups or/and C-H activation reactions. Several novel 5- or 6-membered iridacycles, including bimetallic iridium complexes with a bridge of ten sp~2-carbon chain and an iridaindene complexes, were synthesized and characterized. Furthermore, the thermal and electrochemical properties as well as the reactivity of the bimetallic iridium complexe with a bridge of ten sp~2-carbon chain have also been investigated.
     In chapter 6, the innovation of the dissertation is concluded and the prospect of this research is presented.

引文

[1] Omae,I.Organometallic intramolecular-coordination compounds containing a nitrogen donor ligand [J], Chem.Rev., 1979,79(4): 287-321.
    [2] Bruce M I, Cyclometalation Reactions [J], Angew. Chem. Int. Ed. Engl.,1977, 16(2): 73-86.
    [3] Overman L E, Remarchuk T P, Catalytic Asymmetric Intramolecular Aminopalladation:Enantioselective Synthesis of Vinyl-Substituted 2-Oxazolidinones, 2-Imidazolidinones,and 2-Pyrrolidinones [J], J. Am. Chem. Soc., 2002,124(1): 12-13.
    [4] Djukic J-P, Hijazi A, Flack H D, Bernardinelli G, Non-racemic (scalemic) planar-chiral five-membered metallacycles: routes, means, and pitfalls in their synthesis and characterization [J], Chem. Soc. Rev., 2008,37,406-425.
    [5] Bleeke J R,Aromatic iridacycles [J], Acc.Chem. Res., 2007,40(10): 1035-1047.
    [6] Bleeke J R,Blanchard J M B, Donnay E, Synthesis, Spectroscopy, and Reactivity of a Metallapyrylium[J], Organometallics, 2001,20(2): 324-336.
    [7] Esterulas M A, Lápez A M, Oliván M.Osmium-carbon double bonds: Formation and reactions [J], Coordination Chemistry Reviews, 2007,251,795-840.
    [8] Shilov A E, Shul'pin G B, Activation of C-H Bonds by Metal Complexes [J], Chem. Rev.,1997,97(8): 2879-2932.
    [9] Albrecht M, van Koten G, Platinum Group Organometallics Based on "Pincer" Complexes:Sensors, Switches, and Catalysts [J], Angew. Chem. Int. Ed., 2001,40(20): 3750-3781.
    [10] Trofinenko S, Dipalladiobenzenes [J], J. Am. Chem. Soc, 1971,93(7):1808-1809.
    [11] Rybtchinski B Y, Ben-David Y, Milstein D,Organometallics, 1997, 16(17): 3786-3793.
    [12] Englert U,Podewils F, Schiffers I, Salzer A, The First Homoleptic Metallabenzene Sandwich Complex [J], Angew. Chem., Int. Ed. Engl., 1998,37(15): 2134-2136.
    [13] Effertz U, Englert U, Podewils F, Salzer A, Wagner T,Kaupp M, Reaction of Pentadienyl Complexes with Metal Carbonyls: Synthetic, Structural, and Theoretical Studies of Metallabenzene π-Complexes[J], Organometallics, 2003, 22(2): 264-274.
    [14] Esteruelas M A, Lled6s A, Olivan M, Ofiate E, Tajada M A, Ujaque G, Ortho-CH Activation of Aromatic Ketones, Partially Fluorinated Aromatic Ketones, and Aromatic Imines by a Trihydride-Stannyl-Osmium(IV) Complex [J], Organometallics, 2003, 22(18): 3753-3765.
    [15] Eguillor B, Esteruelas M A, Olivan M, Ofiate E, Cβ-H Activation of Aldehydes Promoted by an Osmium Complex [J], Organometailics, 2004, 23(25): 6015-6024.
    [16 ] Eguillor B, Esteruelas M A, Olivan M, Ofiate E, C(sp~2)-H Activation of RCH=E-py (E = CH, N) and RCH=CHC(O)R' Substrates Promoted by a Highly Unsaturated Osmium-Monohydride Complex [J], Organometailics, 2005,24 (7): 1428-1438.
    [17] Esteruelas M A, Lahoz F J, Ofiate E, Oro L A, Sola E, Carbon-Carbon Coupling and Carbon-Hydrogen Activation Reactions in Bis(triisopropylphosphine)osmium Complexes [J], J. Am. Chem. Soc, 1996, 118 (1): 89-99.
    [18] Li H, Wu Y, Water-soluble 2-arynaphthoxazole palladium (II) complexes as phosphine-free catalysts for the suzuki reaction in aqueous solvent [J], Appl. Organomet. Chem., 2008,22(4): 233-236.
    [19] Yu A, Li J, Cui M, Wu Y, Addition of alylboronic acids to nitiles in aqueous media catalyzed by a 2,2'-bipyridine-cyclopalladated ferrocenylimine complex [J], Synlett, 2007, 19): 3063-3067.
    [20 ] Zhang J, Wu Y, Zhu Z, Ren G, Mark T C W, Song M P, Application of palladacycle catalyst in the synthesis of mono-arylpyridyl bromides [J], Appl. Organomet. Chem., 2007, 21(11): 935-940.
    [21] Mu B, Li T, Xu W, Zeng G, Liu P, Wu Y, Synthesis, characterization, and application in Heck and Suzuki coupling reactions of amphiphilic cyclopalladated ferrocenylimines [J], Tetrahedron, 2007, 63(46): 11475-11488.
    [22] Nemeh S, Jensen C, Binamira-Soriaga E, Kaska W C, Interaction of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}rhodium(I) with hydrocarbons. X-ray molecular structure of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}chlorohydridorhodium(III) [J], Organometailics, 1983,2(10): 1442-1447.
    [23] van der Boom M E, Kraatz H B, Hassner L, Ben-David Y, Milstein D, Carbon-Carbon vs Carbon-Hydrogen Bond Activation by Ruthenium(II) and Platinum(II) in Solution [J], Organometallics, 1999,18(19): 3873-3884.
    [24] van der Boom M E, Kraatz H B, Ben-David Y, Milstein D, Activation of a non-strained C-C bond with plantinum(II) [J], Chem. Commun., 1996, (18): 2167-2170.
    [25] Valk J-M, Boersma J, van Koten G, Selective intramolecular cleavage of the carbon-silicon bond by palladium salts [J], J. Organomet. Chem. 1994, 483(1-2): 213-216.
    [26] Kleinmann J P, Dubeck M, The Preparation of Cyclopentadienyl [o-(Phenylazo)Phenyl]Nickel [J], J. Am. Chem. Soc, 1963, 85(10): 1544-1545.
    [27] van Koten G, Jastrzebski J T B H, Noltes J G, Triorganotin cations stabilized by intramolecular Sn---N coordination; synthesis and characterization of {C,N,N'-2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides [J], J. Organomet. Chem. 1978, 148(3): 233-245.
    [28] Bleeke J R, Blanchard J M B, Synthesis and Reactivity of a Metallapyrylium [J], J. Am. Chem. Soc, 1997, 119(23): 5443-5444.
    
    [29] Bleeke J R. Metallabenzene[J], Chem. Rev., 2001, 101(5): 1205-1227.
    [30] Gilbertson R D, Weakley T J R, Haley M M. Synthesis, characterization, and isomerization of an iridabenzvalene[J], Chem. Eur. J., 2000,6(3): 437-441.
    [31] Wu H -P, Lanza S, Weakley T J R, Haley M M, Metallabenzenes and Valence Isomers. 3. Unexpected Rearrangement of Two Regioisomeric Iridabenzenes to an (η~5-Cyclopentadienyl)iridium(I) Complex [J], Organometallics, 2002,21(14): 2824-2826.
    [32] Gilbertson R D, Lau TLS, Lanza S, Wu H P, Weakley T J R, Haley M M. Synthesis, s pectroscopy, and structure of a family of iridabenzenes generated by the reaction of Vaska-Type complexes with a nucleophilic 3-vinyl-l-cyclopropene[J], Organometallics, 2003, 22(16): 3279-3289.
    
    [33] Wu H P, Weakley T J R, Haley M M. Regioselective formation of β-alkyl-α- phenyliridabenzenes via unsymmetrical 3-vinylcyclopropenes: Probing steric and electronic influences by varying the alkyl ring substituent[J], Chem. Eur. J., 2005, 11(4): 1191-1200.
    [34] Naota T, Takaya H, Murahashi S-I, Ruthenium-Catalyzed Reactions for Organic Synthesis [J], Chem. Rev., 1998, 98(7): 2599-2660.
    [35] Trost B M, Toste F D, Pinkerton A B, Non-Metathesis Ruthenium-Catalyzed C-C Bond Formation [J], Chem. Rev., 2001,101(7): 2067-2096.
    [36] Michael F E, Duncan A P, Sweeney Z K, Bergman R G, Rearrangements and Stereomutations of Metallacycles Derived from Allenes and Imidozirconium Complexes [J], J Am Chem Soc. 2005, 127(6): 1752-1764.
    [37] Kekule F A. Sur la constitution des substances aromatiques[J], Bull. Soc. Chim., 1865, 3(2): 98-111.
    [38] Kekule F A. Note sur quelques produits de substitution de la benzine[J], Bull. Acad. R. Belg., 1865,19:551-563.
    
    [39] Schleyer P V R. Introduction: Aromaticity[J], Chem. Rev., 2001,101(5): 1115-1117.
    [40] Landorf C W, Haley M M. Recent developments in metallabenzene chemistry[J], Angew. Chem. Int. Ed., 2006,45(24): 3914-3936.
    
    [41] Wright L J. Metallabenzenes and metallabenzenoids[J], Dalton Trans., 2006, (15): 1821-1827.
    [42] He G, Xia H, Jia G. Progress in the synthesis and reactivity studies of metallabenzenes[J], Chinese Science Bulletin, 2004,49(15): 1543-1553.
    [43] Thorn D L, Hoffmann R. Delocalization in metallocycles[J], Nouv. J. Chim., 1979, 3(1): 39-45.
    [44] Elliott G P, Roper W R, Waters J M. Metallacyclohexatrienes or 'metallabenzenes'[J], J. Chem. Soc. Chem. Commun., 1982, (14): 811-813.
    [45] Hung W Y, Zhu J, Wen T B, Yu K P, Sung H H Y, Williams I D, Lin Z, Jia G. Osmabenzenes from the reactions of a dicationic osmabenzyne complex[J], J. Am. Chem. Soc, 2006, 128(42): 13742-13752.
    [46] Barrio P, Esteruelas M A, Onate E, Preparation and Characterization of an Isometallabenzene with the Structure of a 1,2,4-Cyclohexatriene [J], J. Am. Chem. Soc., 2004, 126(7): 1946-1947.
    [47] Xia H, He G Zhang H, Wen T B, Sung H H Y, Williams I D, Jia G Osmabenzenes from the reactions of HC=CCH(OH)C=CH with OsX_2(PPh_3)_3 (X =C1, Br) [J], J. Am. Chem. Soc, 2004, 126(22): 6862-6863.
    [48] Rickard C E F, Roper W R, Woodgate S D, Wright L J. Electrophilic aromatic substitution reactions of a metallabenzene: Nitration and halogenation of the osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh3)2] [J], Angew. Chem. Int. Ed., 2000, 39(4): 750-752.
    [49] Gong L, Lin Y, He G Zhang H, Wang H, Wen T B, Xia H, Synthesis and Characterization of an Air-Stable p-Osmaphenol [J], Organometallics, 2008,27(3): 309-311.
    [50] Paneque M, Posadas C M, Poveda M L, Rend6n N, Salazar V, Onate E, Mereiter K, Formation of Unusual Iridabenzene and Metallanaphthalene Containing Electron-Withdrawing Substituents [J], J. Am. Chem. Soc, 2003, 125(33): 9898-9899.
    [51] Alvarez E, Paneque M, Poveda M L, Rend6n N. Formation of iridabenzenes by coupling of iridacyclopentadienes and alkenes[J], Angew. Chem. Int. Ed. Engl., 2006, 45(3): 474-477.
    [52] Jacob V, Weakley T J R, Haley M M. Metallabenzenes and valence isomers. Synthesis and characterization of a platinabenzene[J], Angew. Chem. Int. Ed., 2002,41(18): 3470-3473.
    [53] Paneque M, Posadas C M, Poveda M L, Rend6n N, Santos L L, Alvarez E, Salazar V, Mereiter K, Onate E, Metallacycloheptatrienes of Iridium(III): Synthesis and Reactivity Organometallics, 2007, 26(14): 3403-3415.
    [54] Gilbertson R D, Weakley T J R, Haley M M. Direct synthesis of an iridabenzene from a nucleophilic 3-vinyl-l-cyclopropene[J], J. Am. Chem. Soc, 1999, 121 (11):2597-2598.
    [55] Landorf C W, Jacob V, Weakley T J R, Haley M M. Rational synthesis of platinabenzenes[J], Organometallics, 2004,23(6): 1174-1176.
    [56] Clark G R, Lu G-L, Roper W R, Wright L J, Stepwise Reactions of Acetylenes with Iridium Thiocarbonyl Complexes To Produce Isolable Iridacyclobutadienes and Conversion of These to either Cyclopentadienyliridium or Tethered Iridabenzene Complexes [J], Organometallics, 2007,26(9): 2167-2177.
    [57] Zhang H, Xia H, He G, Ting B W, Gong L, Jia G Synthesis and characterization of stable ruthenabenzenes[J], Angew. Chem. Int. Ed., 2006, 45(18): 2920-2923.
    [58] Liu S H, Ng W S, Chu H S, Wen T B, Xia H P, Zhou Z Y, Lau C P, Jia G A triple-decker complex with a central metallabenzene[J], Angew. Chem. Int. Ed., 2002,41(9): 1589-1591.
    [59] Zhang H, Feng L, Gong L, Wu L, He G, Wen T B, Yang F, Xia H, Synthesis and Characterization of Stable Ruthenabenzenes Starting from HCtCCH(OH)CtCH [J], Organometallics, 2007,26(10): 2705-2713.
    
    [60] Chin C S, Lee H. New iridacyclohexadienes and iridabenzenes by [2+2+1] cyclotrimerization of alkynes and facile interconversion between iridacyclohexadienes and iridabenzenes[J], Chem. Eur. J., 2004, 10(18): 4518-4522.
    [61] Bleeke J R. Metallabenzene chemistry[J], Acc. Chem. Res., 1991, 24(9): 271-277.
    [62] Yand J, Jones W M. Detection of a ruthenabenzene, ruthenaphenoxide, and ruthenaphenanthrene oxide: the first metalla aromatics of a second-row transition metal[J], J.Am. Chem.Soc, 1995,117(38): 9776-9777.
    [63] Wu H P, Lanza S, Weakley T J, Haley M M. Metallabenzenes and valence isomers. 3.Unexpected rearrangement of two regioisomeric iridabenzenes to an (η~5-cyclopentadienyl)iridium(Ⅰ) complex[J], Organometallics, 2002,21(14): 2824-2826.
    [64] Bleeke J R, Behm R. Synthesis, structure, and reactivity of iridacyclohexadienone and iridaphenol complexes[J], J. Am. Chem. Soc, 1997,119(36): 8503-8511.
    [65] Grotjahn D B, Hoerter J M, Hubbard J L, Double C-H Activation during Functionalization of Phenyl(methyl)ketene on Iridium(Ⅰ) Using Alkynes. Synthesis of l,4-Dien-3-ones [J], J. Am.Chem. Soc, 2004, 126(29): 8866-8867.
    [66] Dirnberger T, Werner H, A Series of Hydrido(vinyl)iridium(Ⅲ) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(Ⅰ) Isomers [J], Organometallics,2005,24(21): 5127-5139.
    [67] Bleeke J R,Synthesis and Reactivity of Heteropentadienyl-Transition-Metal Complexes [J],Organometallics, 2005, 24(22):5190-5207.
    [68] Eguillor B, Esteruelas M A, Oliván M, O(?)ate E, C(sp~2)-H Activation of RCH=E-py (E=CH,N) and RCH=CHC(O)R' Substrates Promoted by a Highly Unsaturated Osmium-Monohydride Complex[J],Organometallics, 2005,24(7):1428-1438.
    [69] Li X, Incarvito C D, Vogel T,Crabtree R H, Intramolecular Oxygen Transfer from Nitro Groups to C≡C Bonds Mediated by Indium Hydrides [J], Organometallics, 2005, 24 (13):3066-3073.
    [70] Esteruelas M A, Hernández Y A, López A M, Oliván M, O(?)ate E, Reduction and C(sp~2)-H Bond Activation of Ketones Promoted by a Cyclopentadienyl-Osmium-Dihydride-Dihydrogen Complex [J], Organometallics, 2005,24(24), 5989-6000.
    [71] Esteruelas M A, López A M, Oliván M, Osmium-carbon double bonds: Formation and reactions [J], Coord. Chem. Rev., 2007, 251(5-6): 795-840.
    [72] Li X, Chen P, Faller J W, Crabtree R H, Cycloiridation of α,β-Unsaturated Ketones, Esters,and Acetophenone [J], Organometallics, 2005,24(20): 4810-4815.
    [73] Alías F M, Daff P J, Paneque M, Poveda M L, Carmona E, Pérez P J, Salazar V,Alvarado Y, Atencio R, Sanchez-Delgado, R, C-C Bond-Forming Reactions of IrIII-Alkenyls and Nitriles or Aldehydes: Generation of Reactive Hydride- and Alkyl-Alkylidene Compounds and Observation of a Reversible 1,2-H Shift in Stable Hydride-IrIII Alkylidene Complexes [J], Chem. Eur. J., 2002, 8(22): 5132-5146.
    [74] Ho E N-M, Lin Z, Wong W-T, Synthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands [J], Chem. Eur. J., 2001, 7(1): 258-271.
    [75] Gray S D, Weller K J, Bruck M. A, Briggs P M, Wigley D E, Carbon-Nitrogen Bond Cleavage in an .eta.2(N,C)-Pyridine Complex Induced by Intramolecular Metal-to-Ligand Alkyl Migration: Models for Hydrodenitrogenation Catalysis [J], J. Am. Chem. Soc, 1995, 117(43): 10678-10693.
    [76] Weller K J, Filippov I, Briggs P M, Wigley D E, Pyridine Degradation Intermediates asModels for Hydrodenitrogenation Catalysis: Preparation and Properties of a Metallapyridine Complex [J], Organometallics, 1998, 17(3): 322-329.
    [77] Wen T B, Hung W Y, Sung H H Y, Williams I D, Jia G. Syntheses of metallabenzynes from an allenylcarbene complex[J], J. Am. Chem. Soc., 2005, 127(9): 2856-2857.
    [78] Wen T B, Ng S M, Hung W Y, Zhou Z Y, Lo M F, Shek L-Y, Williams I D, Lin Z, Jia G, Protonation and Bromination of an Osmabenzyne: Reactions Leading to the Formation of New Metallabenzynes [J], J. Am. Chem. Soc, 2003,125, 884-885.
    [79] Wen T B, Zhou Z Y, Jia G, Synthesis and characterization of a metallabenzyne[J], Angew. Chem. Int. Ed., 2001,40(10): 1951-1954.
    [80] Jia G, Progress in the chemistry of metallabenzynes[J], Acc. Chem. Res., 2004, 37(7): 479-486.
    [81] Gong L, Wu L, Lin Y, Zhang H, Yang F, Wen T, Xia H, Synthesis and haracterization of a bimetallic iridium complex with a ten sp -carbon chain bridge [J], Dalton Trans., 2007, 4122-4125.
    [82] Bleeke J R, Behm R, Xie Y -F, Chiang M Y, Robinson K D, Beatty A M. Synthesis, structure, spectroscopy, and reactivity of a metallabenzene[J], Organometallics, 1997, 16(4): 606-623.
    [83] Bleeke, J. R., Bass, L., Xie, Y. -F. et al., Chemistry of an (η~6-Met- allabenzene) metal complex [J], J. Am. Chem. Soc, 1992, 114(11): 4213-4219.
    [84] Bierstedt A, Clark G R,Roper W R, Wright L J, A 2-iridafuran from reaction between a 1-iridaindene and methyl propiolate [J], J.Organomet.Chem.,2006, 691,3846-3852.
    [85] Bleeke J R, New P R, Blanchard J M B, Haile T, Beatty A M, Synthesis of a New Family of Metallafurans from (Oxapentadienyl)metal Precursors [J], Organometallics, 1995, 14 (11):5127-5137.
    [86] Booth B L, Hargreaves R G, Reactions between methyl-, acetyl-, and phenyl-pentacarbonylmanganese and acetylenes [J], J. Chem. Soc.(A) 1970, 308-314.
    [87] Davidson J L, Green M, Nyathi J C, Scott C, Stone F G A, Welch A J, Woodward P,Reactions of acyl- and alkyl-(tricarbonyl)(η~5-cyclopentadienyl)-molybdenum and -tungsten complexes with but-2-yne; molecular structures of [Mo(COXButNC)(η~3-{O·C(O)·CMe·CMe·CMe})(η~5-C_5H_5)] and [Mo·C(O)·C(Me){C(Me)}2C(Me)·C(CF_3)·O(CO)(η~5-C_5H_5)]J.Chem. Soc., Chem. Commun.,1976, (18): 714-715.
    [88] DeShong P, Sidler D R,Rybczynski P J, Slough G A, Rheingold A L, A general method for the preparation of carbonyl compounds and butenolides from organomanganese pentacarbonyl complexes [J], J. Am. Chem. Soc., 1988,110(8): 2575-2585.
    [89]) Espuelas J, Esteruelas M A, Lahoz F J, Oro L A, Valero C, Reactivity of O_5H_4(CO)(PiPr_3)_2 toward terminal alkynes: synthesis and reactions of the alkynyl-dihydrogen complexes O_SH(C_2R)(.eta.~2-H_2)(CO)(PiPr_3)_2 (R=Ph,SiMe_3)[J],Organometallics, 1993, 12(3):663-670.
    [90] Werner H, Weinand R, Otto H, Aromaten(phosphan)metall-komplexe :Ⅺ.Fünfgliedrige osma-heterocyclen durch alkin-insertion in eine O_S---I- oder O_S-H-bindung [J],J.Organomet.Chem.1986,307(l):49-59.
    [91] Herrmann W A, Ziegler M L, Serhadll O,Organometallic chemistry of reactive organic compounds. 41.Metal-induced carbyne/carbene coupling with Buchner's diazo compound [J],Organometallics, 1983, 2(8): 958-962.
    [92] Komiya S,Ito T,Cowie M, Yamamoto A,Ibers J A,Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-Cl,O)tris(triphenylphosphine)ruthenium(Ⅱ) [J], J. Am. Chem. Soc, 1976, 98(13): 3874-3884.
    [93] Dirnberger T, Werner H, A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers [J], Organometallics, 2005,24(21): 5127-5139.
    [94] Li X, Chen P, Faller J W, Crabtree R H, Cycloiridation of a, p-Unsaturated Ketones, Esters, and Acetophenone [J], Organometallics, 2005,24(20): 4810-4815.
    [95] Loewe C, Shklover V, Berke H, Tetracarbonyl(triphenylpropenetriyl)rhenium. A delocalized rhenacyclobutadiene [J], Organometallics, 1991, 10(9): 3396-3399
    [96] Padolik L L, Galluci J C, Wojcicki A, Fischer-type rhenacyclobutadiene complexes: synthesis, structure, and nucleophilic addition/substitution and oxidation reactions [J], J. Am. Chem. Soc., 1993, 115(22): 9986-9996.
    [97] Garrett K E, Sheridan J B, Pourreau D B, Feng W C, Geoffroy G L, Staley D L, Rheingold A L, Transient generation of the reactive carbene complex [Cp(CO)_2W = CH(Tol)]~+ and its reactions with alkynes to form vinylcarbene, allyl, naphthol, diene, and metallafuran complexes [J], J. Am. Chem. Soc., 1989,111(1989): 8383-8391.
    [98] Woodworth B E, Frohnapfel D S, White P S, Templeton J L, Formation of Derivative Carbyne Complexes from Tp'(CO)_2M==CCH_3 (M = Mo, W) [J], Organometallics, 1998, 17(9): 1655-1662.
    [99] Grotjahn D B, Hoerter J M, Hubbard J L, Double C-H Activation during Functionalization of Phenyl(methyl)ketene on Iridium(I) Using Alkynes. Synthesis of l,4-Dien-3-ones [J], J. Am. Chem. Soc, 2004, 126(26): 8866-8867.
    [100] Bruce M I, Hall B C, Skelton B W, White A H, Zaitseva N N, Oligomerisation of alkynes at a pentamethylcyclopentadienylruthenium centre [J], J. Chem. Soc, Dalton Trans. 2000, (14): 2279-2286.
    
    [101] Bahr G, Muller G E, Chem. Ber., 1955, 88,251-264.
    [102] Prokofev A K, Intramolecular Coordination in Organic Derivatives of Non-transition Elements [J], Russ. Chem. Rev., 1976,45(6), 519-543.
    [103] Gruter G-J M, Klink G P M, Akkerman O S, Bickelhaupt F, Intramolecular Coordination in Organometallic Compounds of Groups 2,12, and 13 [J], Chem. Rev., 1995, 95(7): 2405-2456.
    [104] Ryabov A D, Cyclopalladated complexes in organic synthesis [J], Synthesis, 1985, (3): 233-252.
    
    [105] Newkome G R, Puckett W E, Gupta V K, Kiefer G E, Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors [J], Chem. Rev., 1986, 86(2): 451-489.
    
    [106] van Koten G, Tuning the reactivity of metals held in a rigid ligand environment [J], Pure and Applied Chemistry, 1989,61(10): 1681-1694.
    
    [107] Albrecht M, van Koten G, Platinum Group Organometallics Based on "Pincer" Complexes: Sensors, Switches, and Catalysts [J], Angewantde Chemie, International Edition,English, 2001,40(20): 3750-3781.
    
    [108] Gorla F, Venanzi L M, Synthesis of (1R,1'S)- and (1S,1'S),(1R,1'R)- bis[1-(diphenylphosphino)ethyl]benzene derivatives and their cyclometalation reactions with platinum(II) compounds. The x-ray crystal structures of [2,6-bis[(diphenylphosphino)methyl] phenyl]chloropalladium(II), [(1R,1 'S)-2,6-bis[1 -(diphenylphosphino)ethyl]phenyl] hloroplatinum(II), and [(1R, 1 'R),( 1S, 1 'S)-2,6-bis[ 1 -(diphenylphosphino)ethyl]phenyl] hloroplatinum(11) [J], Organometallics, 1994, 13(1): 43-54.
    
    [109] Gorla F, Togni A, Venanzi L M, Synthesis of an Optically Active Platinum(II) Complex Containing a New Terdentate P-C-P Ligand and Its Catalytic Activity in the Asymmetric Aldol Reaction of Methyl Isocyanoacetate. X-ray Crystal Structure of [2,6-Bis[( 1 'S,2'S)-1 '-(diphenylphosphino)-2',3'-O-isopropylidene-2',3'-dihydroxypropyl]phen yl](.eta.l-nitrato)platinum(II) [J], Organometallics, 1994,13(5): 1607-1616.
    
    [110] Pu L, Hasegawa T, Parkin S, Taube H, Conversion of Osmacyclopentatriene to Osmahexatriene by a 1,2-Hydrogen Shift [J], J. Am. Chem. Soc, 1992, 114(19): 7609-7610.
    
    [111] Gariaschelli L, Malatesta M C, Panzeri S, Reactions of Acetylenes with Noble Metal Carbonyl Halides. Structural Analysis of 9. Preparation, Chemical Characterization, and X-ray [ Pt{-C( = O)C( Pr) = C( Pr)C( Pr) = C( Pr)CI)CI]_2 and the Cyclocarbene Derivative [ Pt{CC( Pr) = C( Pr)C( Pr) = C( Pr)O) (PBu_3)_2CI] [ PF_6] [J], Organometallics, 1987, 6(1): 63-12.
    
    [112] Yongskulrote W, Bramlett J M, Mike C A, Durham B, Allison N T, Photochemical Conversion of (q'-6utadienyl)iron Complexes to Hydroxyferrocenes [J], Organometallics, 1989, 8(2): 556-558.
    [113] Hughes R P, Trujillo H A, Gauri A J, Stereoselective Ring Expansion of 3-Vinyl-1-cyclopropenes To Give (q5-Cyclopentadienyl)rutheniuma nd (q4-Cyclohexadienone)ironC omplexes. Exclusion of Planar Metallacyclohexadiene Intermediates and Relevance to the Dtitz Reaction [J], Organometallics, 1996, 14(9): 4319-4324.
    [114] Hughes R P, Robinson D J, Transition-Metal-Promoted Activation of Carbon-Carbon Bonds.A New Synthetic Route to Substituted Ruthenocene Derivatives via Ring Expansion Reactions of 3-Vinyl-I-cyclopropenes [J], Organometallics 1989, 8(4):1015-1019.
    [115] Kiefer E F, Waters W L, Carlson D A, Nuclear magnetic resonance investigation of secondary valence forces. I. Intramolecular n coordination in aralkylmercury compounds [J],J. Am. Chem.Soc,1968,90(19): 5127-5131.
    [116] Pu L, Hasegawa T, Parkin S, Taube H, Osmacyclopentatriene Complexes: Structural Characterization of [O_S(C_4Me_4) (en)_2](CF_3SO_3)_2 [J], J. Am. Chem. Soc, 1992, 114(7):2712-2713.
    [117] Godoy F, Klahn A H, Lahoz F J, Balana A I, Oelckers B, Oro L A, Syntheses and Reactivity of Functionalized (η~5-Tetramethylcyclopentadienyl) Rhenium Complexes: Molecular Structures of (η~5:η~2-C_5Me_4CH_2CH_2CH=CH_2)Re(CO)_2 and (η~5-C_5Me_4CH_2-2-C_4H_3S)Re(CO)_2(PMe_3) [J], Organometallics, 2003, 22(24): 4861-4868.
    [118] Ryabov A D, Insertion of Alkynes into the Pd-C Bond of Palladacycles.Mechanistic Information from High-pressure Kinetic and X-ray Structural Data [J], Organometallics,1993,12(4):1386-1393.
    [119] Rosenthal U, Burlakov V V, Arndt P, Baumann W, Spannenberg A, Five-Membered Titana-and Zirconacyclocumulenes: Stable l-Metallacyclopenta-2,3,4-trienes[J], Organometallics,2005, 24(4): 456-471.
    [120] Rüba E, Mereiter K, Schmid R, Kirchner K, Schottenberger H, The reaction of ferrocenyl acetylene with [RuCp(PR_3)(CH_3CN)_2]PF_6 (R=Me, Ph, Cy).Formation of the first allenyl carbene complexes [J], J. Organomet.Chem.,2001, 637-639,70-74.
    [121] Rüba E, Mereiter K, Schmid R, Sapunov V N, Kirchner K, Schottenberger H, Calhorda M J,Veiros L F, Selective C-C Bond Formation between Alkynes Mediated by the [RuCp(PR_3)]~+ Fragment Leading to Allyl,Butadienyl, and Allenyl Carbene Complexes--An Experimental and Theoretical Study [J], Chem. Eur. J., 2002, 8(17): 3948-3961.
    [122] Wen T B, Hung W Y, Sung H H Y, Williams I D,Jia G,Syntheses of Metallabenzynes from an Allenylcarbene Complex [J], J. Am. Chem.Soc., 2005,127(9): 2856-2857.
    [123] Wen T B, Hung W Y, Zhou Z Y, Lo M F, Williams I D,Jia G,Synthesis and Characterization of [O_SCl_2(=C=CHR)(PPh_3)_2] and Related Complexes [J],Eur.J.Inorg.Chem.,2004,2837-2846.
    [1] Saito S, Yamamoto Y, Recent Advances in the Transition-Metal-Catalyzed Regioselective Approaches to Polysubstituted Benzene Derivatives [J], Chem.Rev.,2000,100(8):2901-2916.
    [2] Lautens M,Klute W,Tarn W,Transition Metal-Mediated Cycloaddition Reactions [J], Chem.Rev., 1996,96(1):49-92.
    [3] Elliott G P, Roper W R, Waters J M. Metallacyclohexatrienes or 'metallabenzenes'[J], J. Chem.Soc.Chem.Commun.,1982,(14): 811-813.
    [4] Hung W Y, Zhu J, Wen T B, Yu K P, Sung H H Y, Williams I D, Lin Z, Jia G. Osmabenzenes from the reactions of a dicationic osmabenzyne complex[J], J. Am. Chem. Soc, 2006,128(42): 13742-13752.
    [5] Barrio P, Esteruelas M A, Onate E, Preparation and Characterization of an Isometallabenzene with the Structure of a 1,2,4-Cyclohexatriene [J], J. Am. Chem. Soc, 2004, 126(7): 1946-1947.
    [6] Xia H, He G, Zhang H, Wen T B, Sung H H Y, Williams I D, Jia G. Osmabenzenes from the reactions of HC=CCH(OH)C=CH with OsX_2(PPh_3)_3 (X =C1, Br) [J], J. Am. Chem. Soc., 2004,126(22): 6862-6863.
    [7] Rickard C E F, Roper W R, Woodgate S D, Wright L J. Electrophilic aromatic substitution reactions of a metallabenzene: Nitration and halogenation of the osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh_3)2] [J], Angew. Chem. Int. Ed., 2000,39(4): 750-752.
    [8] Gong L, Lin Y, He G, Zhang H, Wang H, Wen T B, Xia H, Synthesis and Characterization of an Air-Stable p-Osmaphenol [J], Organometallics, 2008,27(3): 309-311.
    [9] Paneque M, Posadas C M, Poveda M L, Rend6n N, Salazar V, Onate E, Mereiter K, Formation of Unusual Iridabenzene and Metallanaphthalene Containing Electron-Withdrawing Substituents [J], J. Am. Chem. Soc., 2003,125(33): 9898-9899.
    [10] Alvarez E, Paneque M, Poveda M L, Rend6n N. Formation of iridabenzenes by coupling of iridacyclopentadienes and alkenes[J], Angew. Chem. Int. Ed. Engl., 2006,45(3): 474-477.
    [11] Jacob V, Weakley T J R, Haley M M. Metallabenzenes and valence isomers. Synthesis and characterization of a platinabenzene[J], Angew. Chem. Int. Ed., 2002,41(18): 3470-3473.
    [12] Wu H P, Weakley T J R, Haley M M. Regioselective formation of β-alkyl-α- phenyliridabenzenes via unsymmetrical 3-vinylcyclopropenes: Probing steric and electronic influences by varying the alkyl ring substituent[J], Chem. Eur. J., 2005,11(4): 1191-1200.
    [13] Paneque M, Posadas C M, Poveda M L, Rend6n N, Santos L L, Alvarez E, Salazar V, Mereiter K, Onate E, Metallacycloheptatrienes of Iridium(III): Synthesis and Reactivity Organometallics, 2007,26(14): 3403-3415.
    [14] Gilbertson R D, Weakley T J R, Haley M M. Direct synthesis of an iridabenzene from a nucleophilic 3-vinyl-l-cyclopropene[J], J. Am. Chem. Soc, 1999, 121(11):2597-2598.
    [15] Landorf C W, Jacob V, Weakley T J R, Haley M M. Rational synthesis of platinabenzenes[J], Organometallics, 2004,23(6): 1174-1176.
    [16] Clark G R, Lu G-L, Roper W R, Wright L J, Stepwise Reactions of Acetylenes with Iridium Thiocarbonyl Complexes To Produce Isolable Iridacyclobutadienes and Conversion of These to either Cyclopentadienyliridium or Tethered Iridabenzene Complexes [J], Organometallics, 2007, 26(9): 2167-2177.
    [17] Zhang H, Xia H, He G, Ting B W, Gong L, Jia G. Synthesis and characterization of stable ruthenabenzenes[J], Angew. Chem. Int. Ed., 2006,45(18): 2920-2923.
    [18] Liu S H, Ng W S, Chu H S, Wen T B, Xia H P, Zhou Z Y, Lau C P, Jia G. A triple-decker complex with a central metallabenzene[J], Angew. Chem. Int. Ed., 2002,41(9): 1589-1591.
    [19] Gilbertson R D, Lau T L S, Lanza S, Wu H P, Weakley T J R, Haley M M. Synthesis, s pectroscopy, and structure of a family of iridabenzenes generated by the reaction of Vaska-Type complexes with a nucleophilic 3-vinyl-l-cyclopropene[J], Organometallics, 2003, 22(16): 3279-3289.
    [20] Gilbertson R D, Weakley T J R, Haley M M. Synthesis, characterization, and isomerization of an iridabenzvalene[J], Chem. Eur. J., 2000,6(3): 437-441.
    [21] Zhang H, Feng L, Gong L, Wu L, He G, Wen T B, Yang F, Xia H, Synthesis and Characterization of Stable Ruthenabenzenes Starting from HCtCCH(OH)CtCH [J], Organometallics, 2007, 26(10): 2705-2713.
    
    [22] Bleeke J R. Metallabenzene[J], Chem. Rev., 2001, 101(5): 1205-1227.
    [23] Bleeke J R. Aromatic iridacycles[J], Acc. Chem. Res., 2007,40(10): 1035-1047.
    [24] Landorf C W, Haley M M. Recent developments in metallabenzene chemistry[J], Angew. Chem. Int. Ed., 2006,45(24): 3914-3936.
    [25] Wright L J. Metallabenzenes and metallabenzenoids[J], Dalton Trans., 2006, (15): 1821-1827.
    [26] Grotjahn D B, Hoerter J M, Hubbard J L, Double C-H Activation during Functionalization of Phenyl(methyl)ketene on Iridium(I) Using Alkynes. Synthesis of l,4-Dien-3-ones [J], J. Am. Chem. Soc, 2004, 126(29): 8866-8867.
    [27] Dirnberger T, Werner H, A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers [J], Organometallics, 2005, 24(21): 5127-5139.
    [28] Bleeke J R, Synthesis and Reactivity of Heteropentadienyl-Transition-Metal Complexes [J], Organometallics, 2005, 24(22): 5190-5207.
    [29] Eguillor B, Esteruelas M A, Oliván M, O(?)ate E, C(sp~2)-H Activation of RCH=E-py (E=CH,N) and RCH=CHC(O)R' Substrates Promoted by a Highly Unsaturated Osmium-Monohydride Complex[J], Organometallics, 2005,24(7): 1428-1438.
    [30] Li X, Incarvito C D, Vogel T,Crabtree R H, Intramolecular Oxygen Transfer from Nitro Groups to C≡C Bonds Mediated by Iridium Hydrides [J], Organometallics, 2005, 24 (13):3066-3073.
    [31] Esteruelas M A, Hernández Y A, López A M, Oliván M, O(?)ate E, Reduction and C(sp~2)-H,Bond Activation of Ketones Promoted by a Cyclopentadienyl-Osmium-Dihydride-Dihydrogen Complex [J], Organometallics, 2005, 24(24), 5989-6000.
    [32] Esteruelas M A, López A M, Oliván M,Osmium-carbon double bonds:Formation and reactions [J], Coord. Chem.Rev.,2007,251(5-6):795-840.
    [33] Li X, Chen P, Faller J W, Crabtree R H, Cycloiridation of α,β-Unsaturated Ketones, Esters,and Acetophenone [J], Organometallics, 2005, 24(20): 4810-4815.
    [34] Bleeke J R,Blanchard J M B, Synthesis and Reactivity of a Metallapyrylium [J], J. Am.Chem. Soc, 1997, 119(23): 5443-5444.
    [35] Bleeke J R,Blanchard J M B, Donnay E, Synthesis, Spectroscopy, and Reactivity of a Metallapyrylium [J], Organometallics, 2001,20(2): 324-336.
    [36] Alías F M, Daff P J, Paneque M, Poveda M L, Carmona E, Pérez P J, Sálazar V,Alvarado Y,Atencio R, Sdnchez-Delgado, R, C-C Bond-Forming Reactions of IrⅢ-Alkenyls and Nitriles or Aldehydes: Generation of Reactive Hydride- and Alkyl-Alkylidene Compounds and Observation of a Reversible 1,2-H Shift in Stable Hydride-IrⅢ Alkylidene Complexes [J],Chem. Eur. J., 2002, 8(22): 5132-5146.
    [37] Ho E N-M, Lin Z, Wong W-T, Synthesis, Characterisation, Crystal Structures, Reactivity,and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands [J], Chem. Eur. J., 2001,7(1):258-271.
    [38] Gray S D, Weller K J, Bruck M. A, Briggs P M, Wigley D E, Carbon-Nitrogen Bond Cleavage in an.eta.2(N,C)-Pyridine Complex Induced by Intramolecular Metal-to-Ligand Alkyl Migration: Models for Hydrodenitrogenation Catalysis [J], J. Am. Chem. Soc, 1995,117(43): 10678-10693.
    [39] Weller K J, Filippov I, Briggs P M, Wigley D E, Pyridine Degradation Intermediates as Models for Hydrodenitrogenation Catalysis: Preparation and Properties of a Metallapyridine Complex [J], Organometallics, 1998, 17(3): 322-329.
    [40] Wen T B, Hung W Y, Sung H H Y, Williams I D, Jia G. Syntheses of metallabenzynes from an allenylcarbene complex[J], J. Am. Chem. Soc, 2005, 127(9): 2856-2857.
    [41] Wen T B, Ng S M, Hung W Y, Zhou Z Y, Lo M F, Shek L-Y, Williams I D, Lin Z, Jia G, Protonation and Bromination of an Osmabenzyne: Reactions Leading to the Formation of New Metallabenzynes [J], J. Am. Chem. Soc, 2003, 125, 884-885.
    [42] Wen T B, Zhou Z Y, Jia G, Synthesis and characterization of a metallabenzyne[J], Angew. Chem. Int. Ed., 2001,40(10): 1951-1954.
    [43] Jia G, Progress in the chemistry of metallabenzynes[J], Acc. Chem. Res., 2004, 37(7): 479-486.
    [44] Atesin T A, Jones W D, A Deeper Look into Thiophene Coordination Prior to Oxidative Addition of the C-S Bond to Platinum(O): A Computational Study Using DFT and MO Methods [J], Organometallics, 2008,27(1): 53-60.
    [45] Simhai N.; Iverson C N, Edelbach B L, Jones W D, Formation of Phenylene Oligomers Using Platinum-Phosphine Complexes [J], Organometallics, 2001, 20(13): 2759-2766.
    [46] Purohit C S, Verma S, Patterned Deposition of a Mixed-Coordination Adenine-Silver Helicate, Containing a π-Stacked Metallacycle, on a Graphite Surface [J], J. Am. Chem. Soc, 2007, 129(12): 3488-3489.
    [47] Anderson D J, McDonald R, Cowie M, Carbon-Fluorine Bond Activation in Fluoroolefins: Clear Documentation of Cooperative C-F Bond Activation by Adjacent Metal Centers Angew. Chem. Int. Ed., 2007, 46(20): 3741-3744.
    [48] Graham P M, Buschhaus M S A, Legzdines P, Intramolecular C-H Activation Reactions of Molybdenacyclobutanes [J], J. Am. Chem. Soc, 2006, 128(28): 9038-9039.
    [49] Wang Q, Fan H, Xi Z, 1-Zircona-2-cyclohexenes: Novel Synthesis and Preliminary Reactions [J], Organometallics, 2007, 26(4), 775-777.
    [50] Gong L, Wu L, Lin Y, Zhang H, Yang F, Wen T, Xia H, Synthesis and haracterization of a bimetallic iridium complex with a ten sp~2-carbon chain bridge [J], Dalton Trans., 2007, 4122-4125.
    [51] Atesin T A, Oster S S, Skugrud K, Jones W D, The synthesis and structural properties of [M(dippe)(η2-C4H4S)] complexes of Pd and Pt and comparison with their Ni analog [J], Inorg. Chim. Acta., 2006, 359(9): 2798-2805.
    [52] Chanda N, Sharp P R, Bromination of a Naphthalene Platinacycle [J], Organometallics, 2007, 26(14): 3368-3373.
    [53] Vicic D A, Jones W D, Modeling the Hydrodesulfurization Reaction at Nickel. Unusual Reactivity of Dibenzothiophenes Relative to Thiophene and Benzothiophene [J], J. Am. Chem. Soc, 1999, 121(33): 7606-7617.
    [54] Simhai N, Iverson C N, Edelbach B L, Jones W D, Formation of Phenylene Oligomers Using Platinum-Phosphine Complexes [J], Organometallics, 2001, 20(13): 2759-2766.
    [55] Czepa A, Hofmann T, Quantitative Studies and Sensory Analyses on the Influence of Cultivar, Spatial Tissue Distribution, and Industrial Processing on the Bitter Off-Taste of Carrots (Daucus carota L.) and Carrot Products [J], J. Agric. Food. Chem., 2004, 52(14): 4508-4514.
    [56] Balagurova E V, Cheredilin D N, Kolomnikova G D, Tok O L, Dolgushin F M, Yanovsky A I, Chizhevsky I T, Stable exo-mdo-Metallacarboranes (M = Os~(IV)) that Incorporate meta-Carborane-Based Dicarbollide Ligands [J], J. Am. Chem. Soc, 2007, 129(12): 3745-3753.
    [57] Zhang L, Dang L, Wen T B, Sung H H-Y, Williams I D, Lin Z, Jia G, Cyclometalation of 2-Vinylpyridine with MCl_2(PPh_3)_3 and MHCl(PPh_3)_3 (M = Ru, Os) [J], Organometallics, 2007,26(11), 2849-2860.
    [58] Gauvin R M, Rozenberg H, Shimon L J W, Ben-David Y, Milstein D, Osmium-Mediated C-H and C-C Bond Cleavage of a Phenolic Substrate: p-Quinone Methide and Methylene Arenium Pincer Complexes [J], Chem. Eur. J., 2007, 13(5): 1382-1393.
    [59] Wen T B, Zhou Z Y, Lo M F, Williams I D, Jia G, Vinylidene, Allenylidene, and Carbyne Complexes from the Reactions of [OsCl_2(PPh_3)_3] with HCCC(OH)Ph_2 [J], Organometallics 2003, 22(25), 5217-5225.
    [60] Gauvin R M, Rozenberg H, Shimon L J W, Milstein D, Synthesis and Structure of New Osmium-PCP Complexes. Osmium-Mediated C-C Bond Activation [J], Organometallics, 2001,20(9): 1719-1724.
    [61] Jones P R, Caulton K G, Solution structure and dynamics of five-coordinate d6 complexes [J], J. Am. Chem. Soc, 1975,97(15): 4221-4228.
    [62] Gong L, Lin Y, Wen T B, Zhang H, Zeng B, Xia H, Formation of Three Different Conjugated Osmacyclic Species in a One-Pot Reaction [J], Organometallics, 2008,27(11): 2587-2589.
    [63] Bleeke J R, Behm R, Synthesis, Structure, and Reactivity of Iridacyclohexadienone and Iridaphenol Complexes [J], J. Am. Chem. Soc, 1997,119(36): 8503-8511.
    [64] Pu L, Hasegawa T, Parkin S, Taube H, Conversion of osmacyclopentatriene to osmahexatriene via 1,2-hydrogen shift [J], J. Am. Chem. Soc, 1992,114(19) 7609-7910.
    [65] Casey C P, Selmeczy A D, Nash J R, Yi C S, Powell D R, Hayashi R K, Synthesis of η~3-Propargyl Rhenium Complexes [J], J. Am. Chem. Soc, 1996,118(28): 6698-6706.
    [66] LaLonde R L, Sherry B D, Kang E J, Toste F D, Gold(I)-Catalyzed Enantioselective Intramolecular Hydroamination of Allenes [J], J. Am. Chem. Soc, 2007, 129(9): 2452-2453.
    [67] Jiang X, Ma S, trans-RhCl(CO)(PPh_3)_2-Catalyzed Monomeric and Dimeric Cycloisomerization of Propargylic 2,3-Dienoates. Establishment of α,β-Unsaturated δ-Lactone Rings by Cyclometallation [J], J. Am. Chem. Soc, 2007,129(37): 11600-11607.
    [68] Burks H E, Liu S, Morken J P, Development, Mechanism, and Scope of the Palladium-Catalyzed Enantioselective Allene Diboration [J], J. Am. Chem. Soc, 2007, 129(28): 8766-8773.
    [69] Zimmer R, Dinesh C U, Nandanan E, Khan F A, Palladium-Catalyzed Reactions of Allenes [J], Chem. Rev., 2000, 100(8): 3067-3126.
    [70] Ma S, Some Typical Advances in the Synthetic Applications of Allenes [J], Chem. Rev., 2005, 105(7): 2829-2872.
    [71] Sydnes L K, Allenes from Cyclopropanes and Their Use in Organic Synthesis-Recent Developments [J], Chem. Rev., 2003, 103(4): 1133-1150.
    [72] Ma S, Transition Metal-Catalyzed/Mediated Reaction of Allenes with a Nucleophilic Functionality Connected to the a-Carbon Atom [J], Acc. Chem. Res., 2003, 36(9): 701-712.
    [73] Hughes R P, Laritchev R B, Zakharov L N, Rheingold A L, Carbon-Fluorine Bond Activation Coupled with Carbon-Carbon Bond Formation at Iridium. Confirmation of Complete Kinetic Diastereoselectivity at the New Carbon Stereocenter by Intramolecular Trapping Using Vinyl as the Migrating Group [J], J. Am. Chem. Soc, 2005, 127(17): 632-63345.
    [74] Hughes R P, Laritchev R B, Zakharov L N, Rheingold A L, Reductive Activation of Carbon-Fluorine Bonds in Perfluoroalkyl Ligands: An Unexpected Route to the Only Known Tetrafluorobutatriene Transition Metal Complex: Ir(η~5-C_5Me_5)(PMe)3)(2,3-η~2-CF_2=C=C=CF_2) [J], J. Am. Chem. Soc, 2004, 126(8): 2308-2309.
    [75] Hughes R P, Larichev R B, Zakharov L N, Rheingold A L, Carbon-Fluorine Bond Activation Coupled with Alkynyl Migration to Give Fluorinated Allenyl Complexes of Iridium [J], Organometallics, 2006,25(16): 3943-3947.
    [76] Yuan J, Hughes R P, Rheingold A L, The First Example of a Bis(trifluoromethyl)carbene Transition-Metal Complex and Its Reduction to a Perfluoroallene Complex [J], Eur. J. Inorg. Chem., 2007, (30): 4723-4725.
    [77] Casey C P, Boiler T M, Kraft S, Guzei I A, Structural Isomers of Aryl-Substituted η~3-Propargyl Complexes: η~2-l-Metalla(methylene)cyclopropene and η~3-Benzyl Complexes [J], J. Am. Chem. Soc., 2002, 124(44): 13215-13221.
    [78] Mantovani N, Marvelli L, Rossi R, Bertolasi V, Bianchini C, Rios I, Peruzzini M, Addition of E-H Bonds (E = S, N) across the C_α=C_β Bond of the Allenylidene Ligand in [Re{C=C=CPh_2}(CO)_2(triphos)](OSO_2CF_3) (Triphos = MeC(CH_2PPh_2)_3) [J], Organometallics, 2002, 21(12): 2382-2394.
    [79] Werner H, Wiedemann R, Laubender M, Windmuller B, Steinert P, Gevert O, Wolf J, Unusual Pathways for Metal-Assisted C-C and C-P Coupling Reactions Using Allenylidenerhodium Complexes as Precursors [J], J. Am. Chem. Soc., 2002, 124(24): 6966-6980.
    [80] Schafer M, Wolf J, Werner H, Binding Two C_2 Units to an Electron-Rich Transition-Metal Center: The Interplay of Alkyne(alkynyl), Bisalkynyl(hydrido), Alkynyl(vinylidene), Alkynyl(allene), Alkynyl(olefin), and Alkynyl(enyne) Rhodium Complexes [J], Organometallics, 2004,23(24): 5713-5728.
    [81] Bai T, Zhu J, Xue P, Sung H H-Y, Williams I D, Ma S, Lin Z, Jia G, Ligand Effect on the Insertion Reactions of Allenes with MHCl(CO)(PPh_3)_3 and MHCl(PPh_3)_3 (M = Ru, Os) [J], Organometallics, 2007,26(23): 5581-5589.
    [82] Bolano T, Castarlenas R, Esteruelas M A, Onate E, Assembly of an Allenylidene Ligand, a Terminal Alkyne, and an Acetonitrile Molecule: Formation of Osmacyclopentapyrrole Derivatives [J], J. Am. Chem. Soc, 2006,128(12): 3965-3973.
    [83] Asensio A, Buil M L, Esteruelas M A, Onate E, A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η~5-C_5H_5)(C=C=CPh_2)L(P~iPr_3)]PF_6 (L = CO, PHPh_2) [J], Organometallics, 2004, 23(24): 5787-5798.
    [84] Wen T B, Zhou Z Y, Lau C-P, Jia G, Isomerization of CH_3C≡CPh to Phenylallene Promoted by an Osmium Hydride Complex [J], Organometallics, 2000,19(18): 3466-3468.
    [85] Ng S H K, Adams C S, Hayton T W, Legzdins P, Patrick B O, Thermal Activation of Hydrocarbon C-H Bonds Initiated by a Tungsten Allyl Complex [J], J. Am. Chem. Soc, 2003, 125(49): 15210-15223.
    [86] Huang J-H, Luci J J, Lee T-Y, Swenson D C, Jensen J H, Messerle L, A Planar Tetracoordinate Carbon and Unusual Bonding in an Organodimetallic Propynylidene Complex Arising from Double C-H Activation of an Allene Ligand [J], J. Am. Chem. Soc, 2003,125(7): 1688-1689.
    [87] Wigginton J R, Chokshi A, Graham T W, McDonald R, Ferguson M J, Cowie M, Alkyne/Methylene Coupling Reactions at Adjacent Rh/Os Centers: Stepwise Transformations from C_1- through G_4-Bridged Species [J], Organometallics, 2005, 24(26): 6398-6410.
    [88] Chokshi A, Rowsell B D, Trepanier S J, Ferguson M J, Cowie M, Carbon-Carbon Bond Formation by Cumulene Insertion into "Rh(u-CH2)M" Moieties (M = Ru, Os): Roles of the Cumulenes and the Metals in Product Formation [J], Organometallics, 2004, 23(20): 4759-4770.
    [89] Alvarez R, Lera A R, Bimetallic Intermediates in the Formation of Nucleophilic Allenylzincs from Allenylpalladiums: A DFT Study [J], Organometallics, 2007, 26(11): 2799-2802.
    [90] Tsang J Y K, Buschhaus M S A, Legdins P, Patrick B O, Ortho-Selective C-H Activation of Substituted Benzenes Effected by a Tungsten Alkylidene Complex without Substituent Coordination [J], Organometallics, 2006, 25(17): 4215-4225.
    [91] Wen T B, Hung W Y, Sung H H Y, Williams I D, Jia G, Syntheses of Metallabenzynes from an Allenylcarbene Complex [J], J. Am. Chem. Soc., 2005,127(9), 2856-2857.
    [92] RUba E, Mereiter K, Schmid R, Kirchner K, Schottenberger H, Synthesis and X-ray structure of an unexpected bidentate allene-aminocarbene complex of tungsten [J], J. Organomet. Chem. 2005,690(16): 3664-3668.
    [93] RUba E, Mereiter K, Schmid R, Sapunov V N, Kirchner K, Schottenberger H, Calhorda M J, Veiros L F, Selective C-C Bond Formation between Alkynes Mediated by the [RuCp(PR_3)]~+ Fragment Leading to Allyl, Butadienyl, and Allenyl Carbene Complexes - An Experimental and Theoretical Study [J], Chem. Eur. J., 2002, 8(17): 3948-3961.
    [94] Zhu J, Jia G, Lin Z, Understanding Nonplanarity in Metallabenzene Complexes [J], Organometallics, 2007,26(8), 1986-1995.
    [95] ]Yand J, Jones W M, Detection of a ruthenabenzene, ruthenaphenoxide, and ruthenaphenanthrene oxide: the first metalla aromatics of a second-row transition metal [J], J. Am. Chem. Soc., 1995, 117(38): 9776-9777.
    [96] O'Connor J M, Pu L, The First Stable Metallacycle-Carbene Complexes: Structural Characterization ofIr( CR=CRCR=CR)( PPh_3)_2( CO)(=C(CH_2)_3O)~+BF_4~-, R = CO)_2CH_3 [J], J. Am. Chem. Soc, 1987, 109(24): 7578-7579.
    [97] O'Connor J M, Pu L, Rheingold A L, Synthesis, Structure, and Reactivity of Metallacycle-Carbene and -Bis(carbene) Complexes. A New Intramolecular Carbene-Carbene Coupling Process [J], J. Am. Chem. Soc, 1990, 112(17): 6232-6247.
    [98] Poignant G, Nlate S, Guerchais V, Synthesis and Properties of (η~2-C,X) Chelate Arylcarbene Complexes [Fe(C_5Me_5)(1){ η~2-C(OMe)C_6H_4-o-X}][OTf] (L = CO, PMe_3; X = OMe, Cl) [J], Organometallics., 1997, 16(1): 124-132.
    [99] Weller K J, Filippov I, Braggs P M, Wigley D E, Pyridine Degradation Intermediates as Models for Hydrodenitrogenation Catalysis: Preparation and Properties of a Metallapyridine Complex[J], Organometallics, 1998, 17(3): 322-329.
    [100] O'Connor J M, Pu L, Woolard S, Chadha R K, Carbene Ligand Insertion into a Metailacycle Ring: A Metallacyclopentadiee to Metallacyclobutene Conversion [J], J. Am. Chem. Soc, 1990, 112(18): 6731-6732.
    
    [101] Nakazawa H, Yamaguchi Y, Miyoshi K, Formation of a Six-Membered Metailacycle Consisting of Iron, Carbon, Phosphorus, Boron, and Two Oxygens: The First Example of Precedence of Migratory Insertion of CO into an M-C Bond over OR Abstraction from Coordinating Phosphite by BF_3 [J], Organometallics, 1996, 15(22): 4661-4663.
    [102] O'Connor J M, Hiibner K, Closson A, Gantzel P, Synthesis and Solid State Characterization of a Meridional Triphos Iridium Metallacycle-Carbene Complex: [{PhP(CH_2CH_2PPh_2)_2}Ir(CR=CRCR=CR){=C(CH_2)_3O}][BF=] (R = CO~2Me) [J], Organometallics, 2001,20(7): 1482-1485.
    [103] Pu L, Hasegawa T, Parkin S, Taube H, Osmacyclopentatriene Complexes: Structural Characterization of [Os(C_4Me_4)(en)_2](CF_3SO_3)_2 [J], J. Am. Chem. Soc, 1992, 114(7): 2712-2713.
    [104] (η~6-Arene)-Ruthenium(II) Complexes Containing Methanide and Methandiide Anions of Ph_2P(=S)CH_2P(=NR)Ph_2: Unprecedented Insertion of Isocyanide into a Ruthenium-Carbene Bond [J], Organometallics, 2008,27(8): 1809-1822.
    [105] Becker E, Mereiter K, Puchberger M, Schmid Roland, Kirchner K, Metallacyclopentatriene-Butadienyl Carbene Rearrangement in the Oxidative Coupling of Alkynes Mediated by [RuCp(SbR_3)(CH-3CN)_2]~+ (R ) Ph, n-Bu) [J], Organometallics, 2003, 22(10): 2124-2133.
    [106] Liu J, Zhang W-X, Guo X, Hou Z, Xi Z, Isolation and Synthetic Applications of 2,5-Bis(alkynylsilyl) Zirconacyclopentadienes [J], Organometallics, 2007, 26(27): 6812-6820.
    [107] Ison E A, Abboud K A, Boncella J M, Synthesis and Reactivity of Molybdenum Imido Diamido Metallacyclopentenes and Metallacyclopentadienes and the Mechanism of Ethylene Exchange with Metallacyclopentane Complexes [J], Organometallics, 2006, 25(7): 1557-1564.
    [108] O'Connor J M, Closson A, Gantzei P, Hydrotris(pyrazolyl)borate Metallacycles: Conversion of a Late-Metal Metallacyclopentene to a Stable Metallacyclopentadiene-Alkene Complex [J], J. Am. Chem. Soc, 2002, 124(11): 2434-2435.
    [109] Hill A F, Rae A D, Schultz M, Wills A C, Bis(alkynyl), Metallacyclopentadiene, and Diphenylbutadiyne Complexes of Ruthenium [J], Organometallics 2007, 26(6): 1325-1338.
    [110] Takahashi T, Kuzuba Y, Kong F, Nakajima K, Xi Z, Formation of Indene Derivatives from Bis(cyclopentadienyl)titanacyclopentadienes with Alkyl Group Migration via Carbon-Carbon Bond Cleavage [J], J. Am. Chem.Soc, 2005, 127(49): 17188-17189.
    [111] Xi Z, Sato K, Gao Y, Lu J, Takahashi T, Unprecedented Double C-C Bond Cleavage of a Cyclopentadienyl Ligand [J], J. Am. Chem. Soc. 2003,125(32): 9568-9569.
    [112] Byrne L T, Hos J P,Kousantonis G A, Sanford V, Skelton B W, White A H, Carbon Chain Formation on Metallic Arrays.X-ray Structural Determinations of [Ru_4(μ_4-(CCC(CO_2Me)C(CO_2Me))(η-C_5H_4R)_2(μ-CO)(CO)_8],[{Ru(CO)_2(μη-C_5H_5)}_2 {μ-CCC(CO_2Me)=C(CO_2Me)C(O)}],and [{Ru(CO)_2(η-C_5H_5)_2{μ-C=C(CN)_2C=C(CN)_2}] (R=H,Me) [J],Organometallics,2002,21(15):3147-3156.
    [113] O'Connor J M, Hiibner K, Closson A, Gantzei P, Synthesis and Solid State Characterization of a Meridional Triphos Indium Metallacycle-Carbene Complex: [{PhP(CH_2CH_2PPh_2)_2} Ir(CR=CRCR=CR){=C(CH_2)_3O}][BF_4] (R=Co_2Me) [J],Organometallics, 2001, 20(7):1482-1485.
    [1] Thorn D L, Hoffmann R. Delocalization in metallocycles[J], Nouv. J. Chim., 1979, 3(1): 39-45.
    
    [2] Bleeke J R. Metallabenzene[J], Chem. Rev., 2001, 101(5): 1205-1227.
    [3] Landorf C W, Haley M M. Recent developments in metallabenzene chemistry[J], Angew. Chem. Int. Ed., 2006,45(24): 3914-3936.
    
    [4] Wright L J. Metallabenzenes and metallabenzenoids[J], Dalton Trans., 2006, (15): 1821-1827.
    [5] Bleeke J R. Aromatic iridacycles[J], Acc. Chem. Res., 2007,40(10): 1035-1047.
    [6] Iron M A, Lucassen A C B, Cohen H van der, Boom M E, Martin J M L. A Computational Foray into the Formation and Reactivity of Metallabenzenes[J], J. Am. Chem. Soc, 2004, 126(37):11699-11710.
    [7] Elliott G P, Roper W R,Waters J M. Metallacyclohexatrienes or 'metallabenzenes'[J], J. Chem.Soc.Chem. Commun., 1982, (14): 811-813.
    [8] Hung W Y, Zhu J, Wen T B, Yu K P, Sung H H Y, Williams I D, Lin Z, Jia G Osmabenzenes from the reactions of a dicationic osmabenzyne complex[J], J. Am. Chem. Soc, 2006, 128(42):13742-13752.
    [9] Rickard C E F, Roper W R, Woodgate S D, Wright L J. Electrophilic aromatic substitution reactions of a metallabenzene: Nitration and halogenation of the osmabenzene [O_S{C(SMe)CHCHCHCH}I(CO)(PPh_3)_2] [J], Angew. Chem. Int. Ed., 2000, 39(4): 750-752.
    [10] Xia H,He G,Zhang H, Wen T B, Sung H H Y, Williams I D, Jia G. Osmabenzenes from the reactions of HC≡CCH(OH)C≡CH with O_SX_2(PPh_3)_3 (X=Cl, Br) [J], J. Am. Chem. Soc,2004, 126(22): 6862-6863.
    [11] Dean J A, Lange's Handbook of Chemistry [B], McGraw-Hill: New York, 1998; Chapter 4.39.
    [12] Gong L, Lin Y, He G, Zhang H, Wang H, Wen T B, Xia H, Synthesis and Characterization of an Air-Stable p-Osmaphenol [J],Organometallics, 2008, 27(3): 309-311.
    [13] Bleeke J R,Behm R. Synthesis, structure, and reactivity of iridacyclohexadienone and iridaphenol complexes[J],J. Am. Chem. Soc, 1997, 119(36): 8503-8511.
    [14] Crocker M, Dunne B J, Green M, Orpen A G, J. Chem. Soc. Dalton Trans., 1991, 1589.
    [15] Yongskulrote W, Bramlett J M, Mike C A, Durham B, Allison N T, Photochemical conversion of (.eta.l-butadienyl)iron complexes to hydroxyferrocenes[J], Organometallics,1989, 8(2): 556-558.
    [16] Garlaschelli L, Malatesta M C, Panzeri S, Reactions of acetylenes with noble metal carbonyl halides. 9. Preparation,chemical characterization and x-ray structural analysis of [cyclic] [Pt{C(O)CPr:CPrCPr:CPrCl}Cl]_2 and the cyclocarbene derivative [Pt{CCPr:CPrCPr:CPrO}(PBu_3)_2Cl][PF6] [J], Organometallics, 1987, 6(1): 63-72.
    [17] Brammer L, Crocker M, Dunne B J, Green M, Morton C E, Nagle K R,Orpen A G, The reactions of σ,η~3-butadienylruthenium complexes with donor ligands and protons: structures of [RuC(Ph)=C(Ph)-η~2-{(Z)-C(Ph)=CH(Ph)}{P(OMe)_3}(η-C_5H_5)] and [RuC(O)C(Ph)=C(Ph)-η~2-{(Z)-C(Ph)=CH(Ph)}{P(OMe)_3}(η-C_5H_5)] [J], J.Chem. Soc, Chem. Commun., 1986, 1226-1228.
    [18] Schultz A G, Harrington R E, Substituent effects on the photorearrangements of 4-alkoxy-4-carbomethoxy-3-methoxy-2,5-cyclohexadien-l-ones [J], J. Org. Chem.,1991,56(22): 6391-6394.
    [19] Baldwin J E, Keliher E J, Activation Parameters for Three Reactions Interconverting Isomeric 4- and 6-Deuteriobicyclo[3.1.0]hex-2-enes [J], J. Am. Chem. Soc, 2002,124(3), 380-381.
    [20] Marchueta I, Olivella S, Sola L, Moyano A, Pericas M A, Riera A, Photochemistry of 3-Substituted Bicyclo[3.1.0]hex-3-en-2-ones. Regioselective Synthesis of Ortho-Substituted Phenols by Pauson-Khand Reaction [J], Org. Lett. 2001, 3(20),3197-3200.
    [21] Zimmerman H E, Alabugin I V, Excited State Energy Distribution and Redistribution and Chemical Reactivity; Mechanistic and Exploratory Organic Photochemistry~(1,2) [J], J. Am.Chem. Soc.,2000, 122(5), 952-953.
    [22] Gσmez I,Olivella S, Reguero M, Riera A, Sole A, Thermal and Photochemical Rearrangement of Bicyclo[3.1.0]hex-3-en-2-one to the Ketonic Tautomer of Phenol.Computational Evidence for the Formation of a Diradical Rather than a Zwitterionic Intermediate [J], J. Am. Chem. Soc, 2002, 124(51), 15375-15384.
    [23] Werner H, Dirnberger T, Schulz M. Synthesis of octahedral hydrido(vinyl)iridium(Ⅲ) complexes by C-H activation: An example of a thermodynamically favored rearrangement [M(CHR=CHX)]→[M(H)(CR=CHX)][J], Angew. Chem., Int. Ed., 1998,27(7):948-950.
    [24] Sunley G J, Menanteau P d C, Adams H, Bailey N A, Maitlis P M. Cyclometallation of unsaturated carboxylic acids by pentamethylcyclopentadienyl-rhodium and -iridium complexes. Crystal structures of [(C_5Me_5)Ir(CPh=CHCO-OXMe_2SO)] and [(C_5Me_5)Ir(CPh=CHCO-OMe)I] [J], J. Chem. Soc. Dalton Trans.,1989, 2415-2421.
    [25] Bierstedt A, Clark G R,Roper W R, Wright L J. A 2-iridafuran from reaction between a 1-iridaindene and methyl propiolate[J], J. Organomet.Chem.,2006,691,3846-3852.
    [26] Bleeke J R, New P R,Blanchard J M B, Haile T, Beatty A M. Synthesis of a new family of metallafurans from (oxapentadienyl)metal precursors[J], Organometallics, 1995, 14(11):5127-5137.
    [27] Yand J, Jones W M. Detection of a ruthenabenzene, ruthenaphenoxide, and ruthenaphenanthrene oxide: the first metalla aromatics of a second-row transition metal[J], J. Am. Chem. Soc, 1995,117(38): 9776-9777.
    [28] Ferede R, Hinton J F, Korfmacher W A, Freeman J P, Allison N T, Possible formation of rhenabenzene. Lithium-halogen exchange reactions in .eta.l-4-bromo-l,4-diphenyl-l,3-butadienyl ligands to form rhenabenzene and ferrabenzene [J], Organometallics, 1985,4(3), 614-616.
    [29] Ferede R, Allison N T, Possible formation of ferrabenzene and its novel conversion to 1,3-diphenyl-2-methoxyferrocene [J], Organometallics, 1983, 2(3): 463-465.
    [30] Yang J, Yin J, Abboud K A, Jones W M, Metallaindenes of Molybdenum, Tungsten, and Ruthenium [J], Organometallics, 1994,13(3): 971-978.
    [31] Peacock A F A, Habtemariam A, Ferna'ndez R, Walland V, Fabbiani F P A, Parsons S, Aird R E, Jodrell D I, Sadler P, Tuning the Reactivity of Osmium(II) and Ruthenium(II) Arene Complexes under Physiological Conditions [J], J. Am. Chem. Soc, 2006,128(5): 1739-1748.
    [32] McQueen J S, Nagao N, Eberspacher T, Li Z W, Taube H, Synthesis and Characterization of trans-[Os(en)_2py(H)]~(2+) and Related Studies [J], Inorg. Chem., 2003,42(12): 3815-3821.
    [33] Murmann R K, Barnes C L, Reaction of [Os(en)_2O_2]~(2+) with Photolyzed [Mo(CN)_8]~(4-) in Water [J], Inorg. Chem., 2001, 40(25): 6514-6517.
    [34] Liu J, Zhang W-X, Guo X, Hou Z, Xi Z, Isolation and Synthetic Applications of 2,5-Bis(alkynylsilyl) Zirconacyclopentadienes [J], Organometallics, 2007,26(27): 6812-6820.
    [35] Ison E A, Abboud K A, Boncella J M, Synthesis and Reactivity of Molybdenum Imido Diamido Metallacyclopentenes and Metallacyclopentadienes and the Mechanism of Ethylene Exchange with Metallacyclopentane Complexes [J], Organometallics, 2006, 25(7): 1557-1564.
    [36] O'Connor J M, Closson A, Gantzei P, Hydrotris(pyrazolyl)borate Metallacycles: Conversion of a Late-Metal Metallacyclopentene to a Stable Metallacyclopentadiene-Alkene Complex [J], J. Am. Chem. Soc, 2002, 124(11): 2434-2435.
    [37] Hill A F, Rae A D, Schultz M, Wills A C, Bis(alkynyl), Metallacyclopentadiene, and Diphenylbutadiyne Complexes of Ruthenium [J], Organometallics, 2007,26(6): 1325-1338.
    [38] Takahashi T, Kuzuba Y, Kong F, Nakajima K, Xi Z, Formation of Indene Derivatives from Bis(cyclopentadienyl)titanacyclopentadienes with Alkyl Group Migration via Carbon-Carbon Bond Cleavage [J], J. Am. Chem. Soc, 2005, 127(49): 17188-17189.
    
    [39] Xi Z, Sato K, Gao Y, Lu J, Takahashi T, Unprecedented Double C-C Bond Cleavage of a Cyclopentadienyl Ligand [J], J. Am. Chem. Soc, 2003,125(32): 9568-9569.
    [40] Shima T, Ichikawa T, Suzuki H, Reaction of a Heterobimetallic Polyhydrido Cluster, [Cp*Ru(η-H)_4OsCp*] (Cp* = η~5-C_5Me_5), with Diphenylacetylene. Regioselective C-H Bond Activation at the Osmium Center [J], Organometallics, 2007,26(25): 6329-6337.
    [41] Adams R D, Qu B, Smith M D, Albright T A, Syntheses, Structures, Bonding, and Redox Behavior of 1,4-Bis(ferrocenyl)butadiyne Coordinated Osmium Clusters [J], Organometallics, 2002,21(14): 2970-2978.
    [42] Yeh W-Y, Shiue T-W, Syntheses of Beltlike Polycyclodiynes Intercalated with Triosmium Carbonyl Clusters [J], Organometallics, 2003,22(14): 2990-2995.
    [1] Elliott G P, Roper W R, Waters J M, Metallacyclohexatrienes or 'metallabenzenes'[J], J. Chem.Soc.Chem. Commun., 1982, (14): 811-813.
    [2] Hung W Y, Zhu J, Wen T B, Yu K P,Sung H H Y,Williams I D, Lin Z, Jia G Osmabenzenes from the reactions of a dicationic osmabenzyne complex[J], J. Am. Chem. Soc., 2006,128(42): 13742-13752.
    [3] Barrio P, Esteruelas M A, O(?)ate E, Preparation and Characterization of an Isometallabenzene with the Structure of a 1,2,4-Cyclohexatriene [J], J. Am. Chem. Soc, 2004,126(7):1946-1947.
    [4] Xia H, He G, Zhang H, Wen T B, Sung H H Y,Williams I D, Jia G. Osmabenzenes from the reactions of HC≡CCH(OH)C≡CH with O_SX_2(PPh_3)_3 (X =C1, Br) [J], J. Am. Chem. Soc.,2004, 126(22): 6862-6863.
    [5] Gong L, Lin Y, He G, Zhang H, Wang H, Wen T B, Xia H, Synthesis and Characterization of an Air-Stable p-Osmaphenol [J], Organometallics, 2008, 27(3): 309-311.
    [6] Paneque M, Posadas C M, Poveda M L, Rend6n N, Salazar V, Onate E, Mereiter K, Formation of Unusual Iridabenzene and Metallanaphthalene Containing Electron-Withdrawing Substituents [J], J. Am. Chem. Soc., 2003, 125(33): 9898-9899.
    [7] Alvarez E, Paneque M, Poveda M L, Rend6n N. Formation of iridabenzenes by coupling of iridacyclopentadienes and alkenes[J], Angew. Chem. Int. Ed. Engl., 2006,45(3): 474-477.
    [8] Jacob V, Weakley T J R, Haley M M. Metallabenzenes and valence isomers. Synthesis and characterization of a platinabenzene[J], Angew. Chem. Int. Ed., 2002,41(18): 3470-3473.
    [9] Wu H P, Weakley T J R, Haley M M. Regioselective formation of β-alkyl-α- phenyliridabenzenes via unsymmetrical 3-vinylcyclopropenes: Probing steric and electronic influences by varying the alkyl ring substituent[J], Chem. Eur. J., 2005, 11(4): 1191-1200.
    [10] Paneque M, Posadas C M, Poveda M L, Rend6n N, Santos L L, Alvarez E, Salazar V, Mereiter K, Onate E, Metallacycloheptatrienes of Iridium(III): Synthesis and Reactivity Organometallics, 2007,26(14): 3403-3415.
    [11] Gilbertson R D, Weakley T J R, Haley M M. Direct synthesis of an iridabenzene from a nucleophilic 3-vinyl-l-cyclopropene[J], J. Am. Chem. Soc, 1999, 121 (11):2597-2598.
    
    [12] Landorf C W, Jacob V, Weakley T J R, Haley M M. Rational synthesis of platinabenzenes[J], Organometallics, 2004,23(6): 1174-1176.
    [13] Clark G R, Lu G-L, Roper W R, Wright L J, Stepwise Reactions of Acetylenes with Iridium Thiocarbonyl Complexes To Produce Isolable Iridacyclobutadienes and Conversion of These to either Cyclopentadienyliridium or Tethered Iridabenzene Complexes [J], Organometallics, 2007, 26(9): 2167-2177.
    [14] Zhang H, Xia H, He G, Ting B W, Gong L, Jia G Synthesis and characterization of stable ruthenabenzenes[J], Angew. Chem. Int. Ed., 2006, 45(18): 2920-2923.
    [15] Rickard C E F, Roper W R, Woodgate S D, Wright L J, Electrophilic aromatic substitution reactions of a metallabenzene: Nitration and halogenation of the osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh3)2] [J], Angew. Chem. Int. Ed., 2000, 39(4): 750-752.
    [16] Zhang H, Feng L, Gong L, Wu L, He G, Wen, T. B.; Yang, F.; Xia, H. Synthesis and Characterization of Stable Ruthenabenzenes Starting from HCtCCH(OH)CtCH [J], Organometallics, 2007, 26(10): 2705-2713.
    
    [17] Bleeke J R, Metallabenzene[J], Chem. Rev., 2001, 101 (5): 1205-1227.
    [18] Bleeke J R, Aromatic iridacycles[J], Acc. Chem. Res., 2007,40(10): 1035-1047.
    [19] Landorf C W, Haley M M, Recent developments in metallabenzene chemistry[J], Angew. Chem. Int. Ed., 2006,45(24): 3914-3936.
    [20] Bleeke J R, Behm R, Xie Y-F, Chiang M Y, Robinson K D, Beatty A M, Synthesis, Structure, Spectroscopy, and Reactivity of a Metallabenzene [J], Organometallics, 1997, 16(4): 606-623.
    [21] Englert U, Podewils F, Schiffers I, Salzer A, The First Homoleptic Metallabenzene Sandwich Complex [J], Angew. Chem., Int. Ed. Engl., 1998,37(15): 2134-2136.
    [22] Effertz U, Englert U, Podewils F, Salzer A, Wagner T, Kaupp M, Reaction of Pentadienyl Complexes with Metal Carbonyls: Synthetic, Structural, and Theoretical Studies of Metallabenzene π-Complexes[J], Organometallics, 2003,22(2): 264-274.
    [23] Wender P A, Introduction: Frontiers in Organic Synthesis[J], Chem. Rev. 1996, 96(1): 1-2.
    [24] Lautens M, Klute W, Tarn W. Transition Metal-Mediated Cycloaddition Reactions[J], Chem. Rev. 1996,96(1),49-92.
    [25] Xi Z, Li P, Deoxygenative Cycloaddition of Aldehydes with Alkynes Mediated by AlCb and Zirconium: Formation of Cyclopentadiene Derivatives [J], Angew. Chem. Int. Ed. 2000, 39(16): 2950-2952.
    [26] Nakamoto M, Tilley T D, Reactions of Zirconacyclopentadienes with Nitrosobenzene. Characterization of Zirconacycle Intermediates and Formation of iV-Phenylpyrroles[J], Organometallics, 2001,20(26): 5515-5517.
    [27] Zhao C J, Li P X, Cao X Y, Xi Z, Lewis Acid Mediated Reactions of Zirconacyclopentadienes with Aldehydes: One-Pot Synthetic Route to Indene and Cyclopentadiene Derivatives from Aldehydes and Benzyne or Alkynes [J], Chem. Eur. J. 2002, 8(18): 4292-4298.
    [28] Takahashi T, Kuzuba Y, Kong F, Nakajima K, Xi Z, Formation of Indene Derivatives from Bis(cyclopentadienyl)titanacyclopentadienes with Alkyl Group Migration via Carbon-Carbon Bond Cleavage [J], J. Am. Chem. Soc, 2005, 127(49): 17188-17189.
    [29] Xi Z, Sato K, Gao Y, Lu J, Takahashi T, Unprecedented Double C-C Bond Cleavage of a Cyclopentadienyl Ligand [J], J. Am. Chem. Soc. 2003, 125(32): 9568-9569.
    [30] Quebatte L, Haas M, Solari E, Scopelliti R, Nguyen Q T, Severin K, Atom-Transfer Radical Reactions under Mild Conditions with [{RuCl_2(1,3,5-C_6H_3iPr_3)}_2] and PCy_3 as the Catalyst Precursors [J], Angew. Chem., Int. Ed. Engl. 2005,44(7): 1084-1088.
    [31] Faure M, Maurette L, Donnadieu B, Lavigne G, Reactions of a Transient Carbonyl(chloro)(hydrido)ruthenium(II) Complex with Ethylene, Alkynes, and CO; Chemistry of the New Anion [Ru_2(CO)_4Cl_5]~- [J], Angew. Chem., Int. Ed. Engl. 1999, 38(4):518-522.
    [32] Fabre S, Kalck P, Lavigne G, Generation of Alkyl(dicarbonyl)(chloro)-ruthenium Dimers in the Ruthenium-Catalyzed Addition of Alkyl Formates to Ethylene [J], Angew. Chem., Int. Ed. Engl. 1997,36(10): 1092-1095.
    [33] Bino A, Gorton F A, A linear, trinuclear, mixed-valence chloro complex of ruthenium, [RU3Cl_(12)]~(4-) [J], J. Am. Chem. Soc. 1980, 102(2), 608-611.
    [34] Mashima K, Komura N, Yamagata T, Tani K, Synthesis and Crystal Structure of a Cationic Trinuclear Ruthenium(II) Complex, [Ru_3(μ_2-Cl)_3(μ_3-Cl)_2 {1,2-bis(diphenylphosphino)benzene}_3]PF_6 [J], Inorg. Chem. 1997, 36(13): 2908-2912.
    [35] Bertling U, Englert U, Salzer A, From Triple-Decker to Metallabenzene: A New Generation of Sandwich Complexes [J], Angew. Chem., Int. Ed. Engl. 1994,33(9): 1003-1004.
    [36] Bosch H W, Hund H-U, Nietlispach D, Salzer A, General route to the half-open ruthenium metallocenes C_5Me_5Ru(pentadienyl) and C_5Me_5Ru(diene)Cl. X-ray structures of an optically active half-open metallocene and of a dimetallic ruthenabenzene complex [J], Organometallics, 1992, 11(6): 2087-2098.
    [37] Lin W, Wilson S R, Girolami G S, Carbon-Carbon Bond Formation Promoted by Organoruthenium Complexes. The First Unsubstituted π-Metallabenzene Complex, Cp*_2Ru_2(η~2 :η~5-C_5H_5)(SiMe_3), and Synthesis of the Tetramethyleneethane Complex Cp*_2Ru_2(η~3: η~3-C_6H_8)Cl_4 [J], Organometallics, 1997, 16(11): 2356-2361.
    [38] Liu S H, Ng W S, Chu H S, Wen T B, Xia H P, Zhou Z Y, Lau C P, Jia G, A Triple-Decker Complex with a Central Metallabenzene [J], Angew. Chem., Int. Ed. 2002,41(9): 1589-1591.
    [39] Kralik M S, Rheingold A L, Ernst R D, (Pentadienyl)molybdenum carbonyl chemistry: conversion of a pentadienyl ligand to a coordinated metallabenzene complex [J], Organometallics, 1987,6(12): 2612-2614.
    [40] Kralick M S, Rheingold A L, Hutchinson J P, Freeman J W, Ernst R D, Synthesis, Characterization, and Reaction Chemistry of (Pentadienyl)molybdenum Carbonyl Complexes [J], Organometallics, 1996, 15(2): 551-561.
    [41] Wudl F, Nalewajek D, Rotella F J, Gebert E, Tetraphenylarsonium 1,2,3,4,5-pentakis(methylmercapto)cyclopentadienide[J], J. Am. Chem. Soc. 1981, 103(19): 5885-5890.
    [42] Burk M J, Calabrese J C, Davidson F, Harlow R L, Roe D C, The chemistry of tetrakis(trifluoromethyl) cyclopentadienone[J], J. Am. Chem. Soc. 1991,113(6): 2209-2222.
    [43] Wessel J, Behrens U, Lork E, Mews R, Tris(dimethylamino) sulfonium cyclopentadienide [TAS]~+[C_5H_5]~- and Tris(dimethylamino) sulfoniumpyrrolide [TAS]~+[C_4H_4N]~-:Two Isostructural Salts with "Naked" Anions A- and the "Inverse" Sandwich-Cations [{(Me_2N)_3S}_2A]~+ (A = C_5H_5~-C_4H_4N~-)[J],Angew. Chem. Int. Ed. Engl.1995, 34(4):443-446.
    [44] Etkin N,Ong C M, Stephan D W, Synthesis of 1,2-Cyclopentadienyl Diimine Anions and Their Zirconium Complexes[J], Organometallics, 1998,17(17): 3656-3660.
    [1] Xi Z, Sato K, Gao Y, Lu J, Takahashi T, Unprecedented Double C-C Bond Cleavage of a Cyclopentadienyl Ligand[J], J. Am. Chem. Soc, 2003,125(32): 9568-9569.
    [2] Johnson S A, Liu F-Q, Suh M C, Zurcher S, Haufe M, Mao S S H, Tilley T D, Regioselective Coupling of Pentafluorophenyl Substituted Alkynes: Mechanistic Insight into the Zirconocene Coupling of Alkynes and a Facile Route to Conjugated Polymers Bearing Electron-Withdrawing Pentafluorophenyl Substituents[J], J. Am. Chem. Soc., 2003, 125(14): 4199-4211.
    [3] Takahashi T, Kuzuba Y, Kong F, Nakajima K, Xi Z, Formation of Indene Derivatives from Bis(cyclopentadienyl)titanacyclopentadienes with Alkyl Group Migration via Carbon-Carbon Bond Cleavage[J], J. Am. Chem. Soc., 2005,127(49): 17188-17189.
    [4] Zhao C, Yan J, Xi Z, Lewis Acid Mediated Reactions of Zirconacyclopentenes with Aldehydes Affording Homoallyl Ketones via Oppenauer-Type Oxidation[J], J. Org. Chem., 2003, 68(11): 4355-4360.
    [5] Wang Q, Fan H, Xi Z, 1-Zircona-2-cyclohexenes: Novel Synthesis and Preliminary Reactions[J], Organometallics, 2007,26(4): 775-777.
    [6] Xi Z, Zhang W-X, Song Z, Zheng W, Kong F, Takahashi T, Preparation of Vinyl Allenes from 1 -Lithio-1,3-dienyl Phosphine Oxides and Aldehydes by the Wittig-Horner Reaction[J], J. Org. Chem., 2005, 70(22): 8785-8789.
    
    [7] Bleeke J R, Metallabenzene[J], Chem. Rev., 2001,101(5): 1205-1227.
    [8] Barrio P, Esteruelas M A, Onate E, Preparation and Characterization of an Isometallabenzene with the Structure of a 1,2,4-Cyclohexatriene [J], J. Am. Chem. Soc., 2004, 126(7): 1946-1947.
    [9] Xia H, He G, Zhang H, Wen T B, Sung H H Y, Williams I D, Jia G. Osmabenzenes from the reactions of HC=CCH(OH)C≡CH with OsX_2(PPh_3)_3 (X =Cl, Br) [J], J. Am. Chem. Soc., 2004, 126(22): 6862-6863.
    [10] Alvarez E, Paneque M, Poveda M L, Rendon N, Formation of Iridabenzenes by Coupling of Iridacyclopentadienes and Alkenes[J], Angew. Chem., Int. Ed., 2006,45(3): 474-477.
    
    [11] Zhang H, Xia H, He G, Ting B W, Gong L, Jia G Synthesis and characterization of stable ruthenabenzenes[J], Angew. Chem. Int. Ed., 2006,45(18): 2920-2923.
    
    [12] Wright L J. Metallabenzenes and metallabenzenoids[J], Dalton Trans., 2006, (15): 1821-1827.
    [13] Dixon S, Fillery S M, Kasatkin A, Norton D,Thomas E, Whitby R J, Ring expansion of 5- to 6-member zirconacycles by carbenoid insertion[J], Tetrahedron, 2004,60(6): 1401-1416.
    [14] Norton D, Whitby R J, Griffen E, Insertion of (E)-(1,2-dihalovinyl)lithium and (2-haloethynyl)lithium into zirconacycles[J], Chem. Commun., 2004, (1): 1214-1215.
    [15] Takahashi T, Xi Z, Obora Y, Suzuki N, Intramolecular Coupling of Alkynyl Groups of Bis(alkynyl)silane Mediated by Zirconocene Compounds: Formation of Silacyclobutene Derivatives[J], J. Am. Chem. Soc.,1995, 117(9): 2665-2666.
    [16] Xi Z, Fischer R, Hara R, Sun W, Obora Y, Suzuki N, Nakajima K, Takahashi T, Zirconocene-Mediated Intramolecular Carbon-Carbon Bond Formation of Two Alkynyl Groups of Bis(alkynyl)silanes[J], J. Am. Chem. Soc., 1997, 119(52): 12842-12848.
    [17]Yu T, Deng L, Zhao C, Li Z, Xi Z, Alkyne and ketone induced novel cleavage of a C---C bond and a C---Si bond in zirconacyclobutene-silacyclobutene fused ring compounds[J], Tetrahedron Lett., 2003,44(4): 677-679.
    [18] Sun X, Wang C, Li Z, Zhang S, Xi Z, Zirconocene-Mediated Intermolecular Coupling of One Molecule of Si-Tethered Diyne with Three Molecules of Organonitriles: One-Pot Formation of Pyrrolo[3,2-c]pyridine Derivatives via Cleavage of C≡N Triple Bonds of Organonitriles[J], J. Am.Chem. Soc, 2004, 126(23): 7172-7173.
    [19] Yu T, Sun X, Wang C, Deng L, Xi Z, Zirconocene-Mediated Intermolecular Coupling of Si-tethered Diynes with Alkynes, Ketones, Aldehydes, and Isocyanates by means of Novel Skeletal Rearrangement of Zirconacyclobutene-Silacyclobutene and Zirconacyclohexadiene-Silacyclobutene Fused-Ring Intermediates[J], Chem. Eur. J., 2005, 11(6): 1895-1902.
    [20] Dupuis L, Pirio N, Meunier P, Igau A, Donnadieu B, Majoral J P, Zirconocen-Benzyme-Mediated Intramolecular Coupling of Bis(alkynyl)phosphane: A Way to Mono- and Tricyclic 1,2-Dihydrophosphetes[J], Angew. Chem., Int. Ed., 1997, 36(9): 987-989.
    [21] Pirio N, Bredeau S, Dupuis L, Schutz P, Donnadieu B, Igau A, Majoral J P, Guillemin J C, Meunier P, Intramolecular coupling of acetylenic groups of bis(alkynyl)phosphanes and silanes mediated by benzynezirconocene: a route to new mono- and tricyclic heterocycles[J], Tetrahedron, 2004,60(6): 1317-1327.
    [22] Cadierno V, Zablocka M, Donnadieu B, Igau A, Majoral J P, Skowronska A, Unexpected Formal [1+3] Cycloadditions between Azides and a-Zirconated Phosphanes: A Route to Unprecedented Phosphazide and Iminophosphorane Complexes[J], Chem. Eur. J., 2000, 6(2): 345-352.
    [23] Horacek M, Stepnicka P, Gyepes R, Cisarova I, Kubista J, Lukesova L, Meunier P, Mach K, Nonclassical Bonding in Titanasilacyclohexadiene Compounds Resulting from Highly Methyl-Substituted Titanocene-Bis(trimethylsilyl)ethyne Complexes and Bis((trimethylsilyl)ethynyl)silanes [J], Organometallics, 2005,24(25): 6094-6103.
    [24] Campora J, Buchwald S L, Nonclassical Bonding in Titanasilacyclohexadiene Compounds Resulting from Highly Methyl-Substituted Titanocene-Bis(trimethylsilyl)ethyne Complexes and Bis((trimethylsilyl)ethynyl)silanes[J], Organometallics, 1995,14(25): 2039-2046.
    [25] Hill J E, Balaich G P, Fannick E I, Rothwell R, The chemistry of titanacyclopentadiene rings supported by 2,6-diphenylphenoxide ligation: stoichiometric and catalytic reactivity[J], Organometallics, 1993, 12(8): 2911-2924.
    [26] Aoyagi K, Kasai K, Kondakov D, Hara R, Suzuki N, Takahashi T, Chemoselective functionalization of zirconacyclopentenes[J], Inorg. Chim. Acta., 1994,220(1-2): 319-326.
    [27] Bleeke J R, Hinkle P V, Synthesis, Structure, Spectroscopy, and Reactivity of a Metallathiabenzenel [J], J. Am. Chem. Soc, 1999, 121(3): 595-596.
    
    [28] Chin C S, Lee H, Eum M-S, Iridabenzenes from Iridacyclopentadienes: Unusual C-C Bond Formation between Unsaturated Hydrocarbyl Ligands[J], Organometallics, 205, 24(20): 4849-4852.
    [29] Wang Q, Fan H, Xi Z, l-Zircona-2-cyclohexenes: Novel Synthesis and Preliminary Reactions [J], Organometallics, 2007, 26(4): 775-777.
    [30] Li X, Chianese A R, Vogel T, Crabtree R H, Intramolecular Alkyne Hydroalkoxylation and Hydroamination Catalyzed by Iridium Hydrides [J], Org. Lett, 2005,7(24): 5437-5440.
    [31] Nanishankar H V, Dutta S, Nethaji M, Jagirdar B R, Dynamics of a cis-Dihydrogen/Hydride Complex of Iridium [J], Inorg. Chem, 2005,44(18): 6203-6210.
    [32] Li X, Incarvito C D, Vogel T, Crabtree R H, Intramolecular Oxygen Transfer from Nitro Groups to C≡C Bonds Mediated by Iridium Hydrides [J], Organometallics, 2005, 24(13): 3066-3073.
    [33] Navarro J, Sola E, Martin M, Dobrinovitch I T, Lahoz F J, Oro L A, C-H Activation and C-C Coupling Reactions in 2-Vinylpyridine Cationic Complexes of Iridium [J], Organometallics, 2004,23(8): 1908-1917.
    [34] Li X, Vogel T, Incarvito C D, Crabtree R H, Electronic and Steric Effects in the Insertion of Alkynes into an Iridium(III) Hydride [J], Organometallics, 2005, 24(1): 62-76.
    [35] Han Y, Deng L, Ziegler T, A Density Functional Study of a-Hydride and Methyl Migratory Insertion in CpM(PH_3XCH_2CH_2)R~+ (M = Co, Rh, Ir; R = H, CH_3) [J], J. Am. Chem. Soc, 1997, 119(25): 5939-5945.
    [36] Burrell A K, Roper W R, Tetrafluoroethyl Complexes Derived from Insertion of the Tetrafluoroethylene Ligand into an Iridium-Hydride Bond [J], Organometallics, 1990, 9(6): 1905-1910.
    [37] McGhee W D, Bergman R G, Synthesis of an ( n3-Allyl)( hydrido)iridium Complex and Its Reactions with Arenes and Alkanes. Sequential Intermolecular C-H Oxidative Addition and Hydride-to- Alkene Migratory Insertion Reactions J. Am. Chem. Soc, 1988, 110(13): 4246-4262.
    [38] Gong L, Wu L, Lin Y, Zhang H, Yang F, Wen T, Xia H, Synthesis and haracterization of a bimetallic iridium complex with a ten sp~2-carbon chain bridge [J], Dalton Trans., 2007, 4122-4125.
    
    [39] Vaska L, Hydrido Complexes Of Iridium [J], J. Am. Chem. Soc. 1961, 83(3): 756-756.
    [40] Landau S E, Groh K E, Lough A J, Morris R H, Large Effects of Ion Pairing and Protonic-Hydridic Bonding on the Stereochemistry and Basicity of Crown-, Azacrown-, and Cryptand-222-potassium Salts of Anionic Tetrahydride Complexes of Iridium(III) [J], Inorg. Chem. 2002,41(11): 2995-3007.
    [41] Rigaut S, Olivier C, Costuas K, Choua S, Fadhel O, Massue J, Turek P, Saillard J-Y, Dixneuf P H, Touchard D, C_7 and C_9 Carbon-Rich Bridges in Diruthenium Systems: Synthesis, Spectroscopic, and Theoretical Investigations of Different Oxidation States[J], J. Am. Chem. Soc, 2006, 128(17): 5859-5876.
    [42] Kaim W, Schwederski B, Dogan A, Fiedler J, Kuehl C J, Stang P J, Metalla-Supramolecular Rectangles as Electron Reservoirs for Multielectron Reduction and Oxidation[J],Inorg.Chem., 2002,41(15):4025-4028.
    [43] DeRosa M C, Al-mutlaq F, Crutchley R J, Semiconductor Properties in an Iodine-Doped Platinum(Ⅱ) Dinuclear Complex[J], Inorg. Chem.,2001,40(7):1406-1407.
    [44] Manna J, Kuehl C J, Whiteford J A, Stang P J, Preparation, via Double Oxidative Addition,and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.~(13)C NMR Analysis of the Nature of the Palladium-Carbon Bond[J], Organometallics, 1997, 16(9): 1897-1905.
    [45] Qi H, Gupta A, Noll B C, Snider G L, Lu Y, Lent C, Fehlner T P, Dependence of Field Switched Ordered Arrays of Dinuclear Mixed-Valence Complexes on the Distance between the Redox Centers and the Size of the Counterions[J],J.Am. Chem. Soc., 2005, 127(43):15218-15227.
    [46] Xu G-L, Zou G,Ni Y-H, DeRosa M C, Crutchley R J, Ren T, Polyyn-diyls Capped by Diruthenium Termini: A New Family of Carbon-Rich Organometallic Compounds and Distance-Dependent Electronic Coupling Therein [J], J. Am.Chem. Soc. 2003, 125(33): 10057-10065.
    [47] DeRosa M C, White C A, Evans C E B, Crutchley R J, Infrared Study of the Class Ⅱ/Class Ⅲ Boundary in Mixed-Valence Dinuclear Ruthenium Complexes[J], J. Am. Chem. Soc., 2001,123(7): 1396-1402.
    [48] Guillemot M, Toupet L, Lapinte C, A Four-Oxidation-State Family of Coordinated Carbon:The First Isolable and Crystallographically Characterized Triradical [M]-C_4-[M]~(3+) [J],Organometallics, 1998,17(10), 1928-1930.
    [49] Seetharaman S K, Chung M-C, Englich U, Ruhlandt-Senge K, Sponsler M B,Temperature-Dependent Coordination of Phosphine to Five-Coordinate Alkenylruthenium Complexes[J], Inorg. Chem., 2007, 46(2): 561-567.
    [50] Narvor N L, Toupet L, Lapinte C, Elemental Carbon Chain Bridging Two Iron Centers:Syntheses and Spectroscopic Properties of [Cp~*(dppe)Fe-C4-FeCp~*(dppe)]n+.cntdot.n[PF6]-.X-ray Crystal Structure of the Mixed Valence Complex (n=1) [J],J.Am.Chem.Soc,1995, 117(27): 7129-7138.
    [51] Adams R D, Qu B, Smith M D, Albright T A, Syntheses, Structures, Bonding, and Redox Behavior of 1,4-Bis(ferrocenyl)butadiyne Coordinated Osmium Clusters[J], Organometallics,2002,21(14): 2970-2978.
    [52] Chung M-C, Gu X,Etzenhouser B A, Spuches A M,Rye P T, Seetharaman S K,Rose D J,Zubieta J, Sponsler M B, Intermetal Coupling in [(n~5-C_5R_5)Fe(dppe)]_2(η-CH=CHCH=CH) and in Their Dicationic and Monocationic Mixed-Valence Forms[J], Organometallics, 2003,22(17): 3485-3494.
    [53] Dembinski R, Bartik T, Bartik B, Jaeger M, Gladysz J A, Toward Metal-Capped One-Dimensional Carbon Allotropes: Wirelike C_6-C_(20) Polyynediyl Chains That Span Two Redox-Active (n~5-C_5Me_5)Re(NO)(PPh_3) Endgroups [J], J. Am. Chem.Soc,2000,122(5):810-822.
    [54] Meyer W E, Amoroso A J, Horn C R,Jaeger M, Gladysz J A, Synthesis and Oxidation of Dirhenium C_4,C_6,and C_8 Complexes of the Formula (η~5-C_5Me_5)Re(NO)(PR_3)(C≡C)n(R_3P)(ON)Re(η~5-C_5Me_5) (R=4-C_6H_4R',cC_6H_(11)):In Search of Dications and Radical Cations with Enhanced Stabilities [J], Organometallics, 2001,20(6):1115-1127.
    [55] Paul F, Meyer W E, Toupet L, Jiao H, Gladysz J A, Lapinte C A, "Conjugal" Consanguineous Family of Butadiynediyl-Derived Complexes: Synthesis and Electronic Ground States of Neutral, Radical Cationic, and Dicationic Iron/Rhenium C4 Species [J], J. Am. Chem.Soc.,2000,122(39): 9405-9414.
    [56] Das N, Ghosh A, Arif A M, Stang P J, Self-Assembly of Neutral Platinum-Based Supramolecular Ensembles Incorporating Oxocarbon Dianions and Oxalate [J], Inorg.Chem.,2005, 44(20): 7130-7137.
    [57] Mukherjee P S, Das N, Kryschenko Y K, Arif A M, Stang P J, Design, Synthesis, and Crystallographic Studies of Neutral Platinum-Based Macrocycles Formed via Self-Assembly [J],J.Am.Chem.Soc, 2004, 126(8): 2464-2473.
    [58] Das N, Mukherjee P S, Arif A M, Stang P J, Facile Self-Assembly of Predesigned Neutral 2D Pt-Macrocycles via a New Class of Rigid Oxygen Donor Linkers [J], J. Am. Chem. Soc,2003,125(46): 13950-13951.
    [59] Kuehl C J, Huang S D, Stang P J, Self-Assembly with Postmodification:Kinetically Stabilized Metalla-Supramolecular Rectangles [J], J. Am. Chem. Soc, 2001, 123(39): 9634-9641.
    [60] Tykwinski R R, Stang P J, Preparation of Rigid-Rod, Di- and Trimetallic, .sigma.-Acetylide Complexes of Iridium(III) and Rhodium(III) via Alkynyl(phenyl)iodonium Chemistry [J], Organometailics, 1994, 13(8): 3203-3208.
    [61] Chin C S, Kim M, Lee H, Noh S, Ok K M, Regio- and Stereoselective C-C Bond Formation between Alkynes: Synthesis of Linear Dienynes from Alkynes [J], Organometailics, 2002, 21(22): 4785-4793.
    [62] Bruce M I, Low P J, Costuas K, Halet J-F, Best S P, Heath G A, Oxidation Chemistry of Metal-Bonded C_4 Chains: A Combined Chemical, Spectroelectrochemical, and Computational Study [J], J. Am. Chem. Soc, 2000, 122(9): 1949-1962.
    [63] Bruce M I, Ellis B G, Low P J, Skelton B W, White A H, Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C≡CC≡C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications [J], Organometailics, 2003,22(16): 3184-3198.
    [64] Xu G-L, Crutchley R J, DeRosa M C, Pan Q-J, Zhang H-X, Wang X, Ren T, Strong Electronic Couplings between Ferrocenyl Centers Mediated by Bis-Ethynyl/Butadiynyl Diruthenium Bridges [J], J. Am. Chem. Soc, 2005, 127(38): 13354-13363.
    [65] Jiao H, Costuas K, Gladysz J A, Halet J-F, Guillemot M, Toupet L, Paul F, Lapinte C, Bonding and Electronic Structure in Consanguineous and Conjugal Iron and Rhenium sp Carbon Chain Complexes [MC_4M']~(n+): Computational Analyses of the Effect of the Metal [J], J. Am. Chem. Soc. 2003, 125(31): 9511-9522.
    [66] Stahl J, Bohling J C, Bauer E B, Peters T B, Mohr W, Martin-Alvarez, J M, Hampel F, Gladysz J A, sp Carbon Chains Surrounded by sp3 Carbon Double Helices: A Class of Molecules that are Accessible by Self-Assembly and Models for " Insulated " Molecular-Scale Devices [J], Angew. Chem. Int. Ed. 2002,41(11): 1871-1876.
    [67] Fraysse S, Coudret C, Launay J-P, Molecular Wires Built from Binuclear Cyclometalated Complexes [J], J. Am. Chem. Soc, 2003, 125(19): 5880-5888.
    [68] Weyland T, Ledoux I, Brasselet S, Zyss J, Lapinte C, Nonlinear Optical Properties of Redox-Active Mono-, Bi-, and Trimetallic σ-Acetylide Complexes Connected through a Phenyl Ring in the Cp~*(dppe)Fe Series. An Example of Electro-switchable NLO Response[J], Organometallics, 2000, 19(24): 5235-5237.
    [69] Liu S H, Hu Q Y,Xue P, Wen T B, Williams I D, Jia G,Synthesis and Characterization of C_(10)H_(10)-Bridged Bimetallic Ruthenium Complexes [J], Organometallics, 2005, 24(4):769-772.
    [70] Yuan P, Liu S H, Xiong W,Yin J,Yu G,Sung H Y, Williams I D, Jia G,Synthesis and Characterization of (CH=CH)3-Bridged Heterobimetallic Ferrocene-Ruthenium Complexes [J],Organometallics 2005,24(7): 1452-1457.
    [71] Liu S H, Xia H P, Wen T B, Zhou Z, Jia G,Synthesis and Characterization of Bimetallic Ruthenium Complexes with (CH)_6 and Related Bridges [J], Organometallics 2003, 22(4):737-743.
    [72] Xia H P, Yeung R C Y, Jia G,Synthesis and Characterization of Bimetallic Ruthenium Complexes Bridged with Linear C_4H_4 and C_6H_4O_2 Ligands [J], Organometallics, 1998,17(22): 4762-4768.
    [73] Xia H P, Jia G,C_5H_5-Bridged Dimeric Ruthenium Complexes [J], Organometallics 1997,16(1): 1-4.
    [74] Xia H P, Yeung R C Y, Jia G,Synthesis of Symmetrical C_5H_5-Bridged Dimeric Ruthenium Complexes [J], Organometallics, 1997,16(15):3557-3560.
    [75] Baya M, Esteruelas M A, Hydride-Carbyne to Carbene Transformation in a Cyclopentadienyl-Osmium Complex: An Alternative to the Single Hydride-Ca Migration [J],Organometallics, 2002,21(11):2332-2335.
    [76] Esteruelas M A, López A M, Oliván M, Osmium-carbon double bonds: Formation and reactions [J], Coord. Chem.Rev., 2007, (251): 795-840.