稀土有机化合物和Lewis酸促进的N-H键选择性活化
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摘要
插入反应是金属有机化学中最重要的基元反应之一,也是设计众多金属有机催化反应的基础。N-H键是有机分子中最常见的基团,将不饱和有机小分子插入N-H键是构建C-N键最理想的方法之一。分子内氢胺化／环化反应实现了两个碳-碳不饱和官能团对N-H键的双插入,但是对于碳-杂原子不饱和官能团能否双插入N-H键尚不清楚。另外,与广泛的稀土有机化合物和不饱和官能团的单加成反应相比,迄今鲜有不饱和有机小分子与稀土有机化合物中2个官能团连续加成的例子。为了深入了解稀土金属有机化合物的反应特性,本论文重点探索了稀土诱导的异氰酸酯双插入N-H键反应和异氰酸酯与不同官能团的连续加成反应,以及基于后一反应原理合成六元和五元氮杂环化合物的新方法。主要目标是阐明稀土有机化合物结构与性质的关系,为设计新的稀土及相关金属催化的有机串联反应提供理论参考。全文重点研究了三种类型的新反应,合成和表征了39个新金属有机化合物,其中36个得到晶体结构表征,揭示了多种稀土有机化合物的新反应特性及其受影响的因素。具体成果如下：
1.研究了异氰酸酯和二茂稀土吡啶胺基化合物的插入反应,结果表明异氰酸酯、茂环及吡啶环上取代基的变化和中心稀土金属离子半径大小对反应选择性没有影响,都是高选择性地形成对应的异氰酸酯双插入N-H键产物Cp2Ln[η2:η1－PyNCONRCONHR]。反应机理研究结果显示,该双插入反应是分步进行的,第二步插入反应比第一步插入更容易发生,即使是按1：1计量反应,也是给出双插入产物作为主要产物,但是,异氰酸酯与吡啶胺直接反应只能形成单加成产物。配位HMPA的存在能阻止第二步插入反应发生。此外,与异氰酸酯插入Ln-N键反应不同,在当前体系中过量的RNCO几乎不发生反应,仅有极少量的二聚体产物形成。所有这些表明,金属诱导的配体基N-H多插入反应的潜在优点是插入的不饱和分子数可以通过中心金属的配位饱和性进行调控。有趣的是,我们还发现这些双插入产物与二丙基胺作用时,能够释放1分子的异氰酸酯,形成脲；此外,另一种异氰酸酯还能将被插入异氰酸酯交换出来。这表明该双插入反应具有可逆性,所形成的双插入产物是一种温和的异氰酸酯前驱体。与d-过渡金属有机化合物不同,在稀土体系,可逆插入反应是非常罕见的,发生上述反应的驱动力可能是氮氢质子的流动性。
2.利用Cp3Yb与邻氨基苯甲酰胺反应,合成了一系列桥联胺基酰胺基稀土配合物{CpLn(μ-η2:η2-NHC6H4CONH)[μ3-η1:η1:η2-NHC6H4CONH]LnCp(HMPA)}2 (Ln= Yb(3-1a), Er(3-1b) Y(3-1c))和[Cp2Yb(HMPA)]2(μ-η2:η1-NHC6H4CONH)(3-2)。发现配合物3-1与PhNCO反应,能形成不寻常的喹唑啉二酮双负离子(Qo)配合物{Cp2Ln[μ3-η2:η2:η1-Qo]}3Yb(HMPA)2(Ln=Yb(3-3a),Er(3-3b)Y(3-3c)),表明胺基和酰胺基上的2个NH与同一个异氰酸酯分子进行了连续加成并伴随相继的胺消去反应发生,提供了一种构建喹唑啉二酮配体的新方法。但是,碳化二亚胺仅能与化合物3-1中的苯胺基N-H键加成,形成{Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH])3Ln(HMPA)3(Ln=Yb(3-4a),Er(3-4b),Y(3-4c))。即使在没有HMPA存在情况下,还是只能得到单加成产物{CpLn[μ-η3:η2-NHCOC6H4NC(NHR)NR]}2(R=iPr,Ln=Yb(3-5a),Er(3-5b), Y(3-5c)；R=Cy,Ln=Yb(3-6a),Er(3-6b),Y(3-6c))。3-5在HMPA存在下可以转化成3-4。
3.在试图利用上述稀土促进的异氰酸酯与双NH基加成反应原理设计催化反应时,发现无水InCl3能比稀土化合物更有效地催化邻氨基苄胺与不同碳化二亚胺反应,生成各种2-胺基取代-3,4-二氢喹唑啉,反应均给出较好的收率以及化学选择性,并对该反应机理进行了初步验证。进一步,还确立了无水InCl3催化邻氨基苯酚和邻氨基苯硫酚与碳化二亚胺的环化反应,分别形成2-胺基苯并嗯唑和2-胺基苯并噻唑。此外,无水InCl3还可以催化邻氨基苄胺与烯亚胺的环化反应,生成2-烷基取代-3,4-二氢喹唑啉。
N-H bonds are among the most ubiquitous and inexpensive chemical linkages in nature, the direct conversion of N-H bond to N-C bond through insertion reactions is an efficient and economical strategy for fine chemical production. Although it has been reported that two unsaturated C-C fuctionality can diinsert into one N-H bond in the intramolecular hydroamination/cyclization, the direct diinsertion of C-X fuctionality into one N-H bond is unknown. On the other hand, there have been detailed studies on the reactions of the cumulative double bond molecules (X=C=Y) with organometallic compounds, indicating that both the C=X and the C=Y double bonds can participate in polar addition reactions. However, in most cases only single-addition products are isolated, and the sequential C=X and C=Y bi-addition processes are rarely observed. Therefore, we systematically investigated the selective diinsertion of isocyanate into N-H bond promoted by organolanthanides; furthermore, we also studied the synthesis and reactivity of the bridge amido-amidate lanthanide compounds, and achieved the subsequent addition reaction of two N-H bonds with one cumulene molecule. According to the mechanism of the latter reaction, a novel method has been established for construction of six-or five-nitrogen-containing heteroatom cycles. Collectively, thirty-nine new organolanthanide complexes are synthesized, among which thirty-six structures were determined through X-ray single crystal diffraction analysis. The main achievements are as follows:
First, it has investigated the diinsertion reaction of isocyanates into the N-H bond of pyridylamido lanthanocene complexes. The results indicated that the substituted groups on isocyanates, cyclopentadiene ring, or pyridyl ring and the radii of the center rare earth metals all have no impact on the diinsertion reaction pattern. Moreover, the mechanism of the diinsertion reactions may be step by step mono-insertion process. Even when pyridylamido lanthanocene reacted with 2 equivalent isocyanate also to afford the diinserted products, however, the reaction of isocyanate with 2-pyridylamine only gives the mono-addition product. It was found that the chelating coordination of HMPA can prevent the second insertion. Furthermore, it has been proven that nPr2NH can abstract one PhNCO unit from the diinserted products to form organic urea nPr2NHCONHPh, representing one rare example of selective release of the functional group of ligands in organolanthanide chemistry. These phenomena indicate that the present diinsertion is reversible, and the petus may be the fluxion of the proton. The existence of the ancillary chelating ligand could help to achieve the diinsertion of isocyanates into N-H bonds promoted by organolanthanides, which may give some new ideas for the design of catalytic cycle.
Second,{CpLn(μ-η2:η2-NHC6H4CONH)[μ3-η1:η1:η2-NHC6H4CONH]LnCp (HMPA)}2(Ln= Yb(3-1a), Er(3-1b) Y(3-1c)) were prepared by the protonolysis of Cp3Ln with equivalent o-aminobenzamide in toluene at room temperature, after reacting with equivalent HMPA, respectively. When Cp3Yb reacted with 0.5 equivalent o-aminobenzamide and subsequent with equivalent HMPA to give [Cp2Yb(HMPA)]2(μ-η2:η1-NHC6H4CONH) (3-2). Treatment of 3-1 with four equivalent PhNCO affords the unexpected containing dianonic quinazolinedione (Qo) ligand product{Cp2Ln[μ3-η2:η2:1-Qo]}3Ln(HMPA)2 (Ln= Yb(3-3a), Er(3-3b) Y(3-3c)), demonstrating that the neighboring anionic NH group of amidate participation could lead to unique isocyanate insertion reactivity. Two unsaturated C=N and C=O double bonds of isocyanate may undergo the subsequent addition with the dianionic amino-amidate ligand in the above process. However, when 3-1 reacted with diisopropylcarbodiimide to only give the monoinsertion products {Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH]}3Ln(HMPA)3 (Ln= Yb(3-4a), Er(3-4b), Y(3-4c)), indicating that carbodiimide only insert into one N-H bond of the bridge amido-amidate ligand. The single N-H bond addition product {CpLn[μ-η3:η2-OCNHC6H4NC(NHR)NR]}2 (R=iPr, Ln= Yb (3-5a), Er (3-5b), Y(3-5c); R= Cy, Ln= Yb (3-6a), Er (3-6b), Y(3-6c)) without HMPA can be obtained by in situ reaction. In addition,3-5 can be transformed into 3-4 in the presence of HMPA.
Third, it describes the construction of six-and five-nitrogen-containing heterocycles from the functionalized amines with cumulene double bond molecules catalyzed by Lewis acid. The results showed that anhydrous InCl3 can catalyze not only o-aminobenzylamine with carbodiimides to afford 2-amino-3,4-dihydroquinazolines, but also o-aminophenol or o-aminothiophenol with carbodiimides to afford 2-aminobenzoxazoles and 2-aminobenzothiazoles, respectively. These reactions all gave good or high yields and better selectivity. Both the stability of the products and the basicity of the eliminated amines play important roles on the chemical selectivity. Moreover, the possible mechanism has been identified.
1.研究了异氰酸酯和二茂稀土吡啶胺基化合物的插入反应,结果表明异氰酸酯、茂环及吡啶环上取代基的变化和中心稀土金属离子半径大小对反应选择性没有影响,都是高选择性地形成对应的异氰酸酯双插入N-H键产物Cp2Ln[η2:η1－PyNCONRCONHR]。反应机理研究结果显示,该双插入反应是分步进行的,第二步插入反应比第一步插入更容易发生,即使是按1：1计量反应,也是给出双插入产物作为主要产物,但是,异氰酸酯与吡啶胺直接反应只能形成单加成产物。配位HMPA的存在能阻止第二步插入反应发生。此外,与异氰酸酯插入Ln-N键反应不同,在当前体系中过量的RNCO几乎不发生反应,仅有极少量的二聚体产物形成。所有这些表明,金属诱导的配体基N-H多插入反应的潜在优点是插入的不饱和分子数可以通过中心金属的配位饱和性进行调控。有趣的是,我们还发现这些双插入产物与二丙基胺作用时,能够释放1分子的异氰酸酯,形成脲；此外,另一种异氰酸酯还能将被插入异氰酸酯交换出来。这表明该双插入反应具有可逆性,所形成的双插入产物是一种温和的异氰酸酯前驱体。与d-过渡金属有机化合物不同,在稀土体系,可逆插入反应是非常罕见的,发生上述反应的驱动力可能是氮氢质子的流动性。
2.利用Cp3Yb与邻氨基苯甲酰胺反应,合成了一系列桥联胺基酰胺基稀土配合物{CpLn(μ-η2:η2-NHC6H4CONH)[μ3-η1:η1:η2-NHC6H4CONH]LnCp(HMPA)}2 (Ln= Yb(3-1a), Er(3-1b) Y(3-1c))和[Cp2Yb(HMPA)]2(μ-η2:η1-NHC6H4CONH)(3-2)。发现配合物3-1与PhNCO反应,能形成不寻常的喹唑啉二酮双负离子(Qo)配合物{Cp2Ln[μ3-η2:η2:η1-Qo]}3Yb(HMPA)2(Ln=Yb(3-3a),Er(3-3b)Y(3-3c)),表明胺基和酰胺基上的2个NH与同一个异氰酸酯分子进行了连续加成并伴随相继的胺消去反应发生,提供了一种构建喹唑啉二酮配体的新方法。但是,碳化二亚胺仅能与化合物3-1中的苯胺基N-H键加成,形成{Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH])3Ln(HMPA)3(Ln=Yb(3-4a),Er(3-4b),Y(3-4c))。即使在没有HMPA存在情况下,还是只能得到单加成产物{CpLn[μ-η3:η2-NHCOC6H4NC(NHR)NR]}2(R=iPr,Ln=Yb(3-5a),Er(3-5b), Y(3-5c)；R=Cy,Ln=Yb(3-6a),Er(3-6b),Y(3-6c))。3-5在HMPA存在下可以转化成3-4。
3.在试图利用上述稀土促进的异氰酸酯与双NH基加成反应原理设计催化反应时,发现无水InCl3能比稀土化合物更有效地催化邻氨基苄胺与不同碳化二亚胺反应,生成各种2-胺基取代-3,4-二氢喹唑啉,反应均给出较好的收率以及化学选择性,并对该反应机理进行了初步验证。进一步,还确立了无水InCl3催化邻氨基苯酚和邻氨基苯硫酚与碳化二亚胺的环化反应,分别形成2-胺基苯并嗯唑和2-胺基苯并噻唑。此外,无水InCl3还可以催化邻氨基苄胺与烯亚胺的环化反应,生成2-烷基取代-3,4-二氢喹唑啉。
N-H bonds are among the most ubiquitous and inexpensive chemical linkages in nature, the direct conversion of N-H bond to N-C bond through insertion reactions is an efficient and economical strategy for fine chemical production. Although it has been reported that two unsaturated C-C fuctionality can diinsert into one N-H bond in the intramolecular hydroamination/cyclization, the direct diinsertion of C-X fuctionality into one N-H bond is unknown. On the other hand, there have been detailed studies on the reactions of the cumulative double bond molecules (X=C=Y) with organometallic compounds, indicating that both the C=X and the C=Y double bonds can participate in polar addition reactions. However, in most cases only single-addition products are isolated, and the sequential C=X and C=Y bi-addition processes are rarely observed. Therefore, we systematically investigated the selective diinsertion of isocyanate into N-H bond promoted by organolanthanides; furthermore, we also studied the synthesis and reactivity of the bridge amido-amidate lanthanide compounds, and achieved the subsequent addition reaction of two N-H bonds with one cumulene molecule. According to the mechanism of the latter reaction, a novel method has been established for construction of six-or five-nitrogen-containing heteroatom cycles. Collectively, thirty-nine new organolanthanide complexes are synthesized, among which thirty-six structures were determined through X-ray single crystal diffraction analysis. The main achievements are as follows:
First, it has investigated the diinsertion reaction of isocyanates into the N-H bond of pyridylamido lanthanocene complexes. The results indicated that the substituted groups on isocyanates, cyclopentadiene ring, or pyridyl ring and the radii of the center rare earth metals all have no impact on the diinsertion reaction pattern. Moreover, the mechanism of the diinsertion reactions may be step by step mono-insertion process. Even when pyridylamido lanthanocene reacted with 2 equivalent isocyanate also to afford the diinserted products, however, the reaction of isocyanate with 2-pyridylamine only gives the mono-addition product. It was found that the chelating coordination of HMPA can prevent the second insertion. Furthermore, it has been proven that nPr2NH can abstract one PhNCO unit from the diinserted products to form organic urea nPr2NHCONHPh, representing one rare example of selective release of the functional group of ligands in organolanthanide chemistry. These phenomena indicate that the present diinsertion is reversible, and the petus may be the fluxion of the proton. The existence of the ancillary chelating ligand could help to achieve the diinsertion of isocyanates into N-H bonds promoted by organolanthanides, which may give some new ideas for the design of catalytic cycle.
Second,{CpLn(μ-η2:η2-NHC6H4CONH)[μ3-η1:η1:η2-NHC6H4CONH]LnCp (HMPA)}2(Ln= Yb(3-1a), Er(3-1b) Y(3-1c)) were prepared by the protonolysis of Cp3Ln with equivalent o-aminobenzamide in toluene at room temperature, after reacting with equivalent HMPA, respectively. When Cp3Yb reacted with 0.5 equivalent o-aminobenzamide and subsequent with equivalent HMPA to give [Cp2Yb(HMPA)]2(μ-η2:η1-NHC6H4CONH) (3-2). Treatment of 3-1 with four equivalent PhNCO affords the unexpected containing dianonic quinazolinedione (Qo) ligand product{Cp2Ln[μ3-η2:η2:1-Qo]}3Ln(HMPA)2 (Ln= Yb(3-3a), Er(3-3b) Y(3-3c)), demonstrating that the neighboring anionic NH group of amidate participation could lead to unique isocyanate insertion reactivity. Two unsaturated C=N and C=O double bonds of isocyanate may undergo the subsequent addition with the dianionic amino-amidate ligand in the above process. However, when 3-1 reacted with diisopropylcarbodiimide to only give the monoinsertion products {Cp2Ln[μ-η3:η1-iPrNC(NHiPr)NC6H4CONH]}3Ln(HMPA)3 (Ln= Yb(3-4a), Er(3-4b), Y(3-4c)), indicating that carbodiimide only insert into one N-H bond of the bridge amido-amidate ligand. The single N-H bond addition product {CpLn[μ-η3:η2-OCNHC6H4NC(NHR)NR]}2 (R=iPr, Ln= Yb (3-5a), Er (3-5b), Y(3-5c); R= Cy, Ln= Yb (3-6a), Er (3-6b), Y(3-6c)) without HMPA can be obtained by in situ reaction. In addition,3-5 can be transformed into 3-4 in the presence of HMPA.
Third, it describes the construction of six-and five-nitrogen-containing heterocycles from the functionalized amines with cumulene double bond molecules catalyzed by Lewis acid. The results showed that anhydrous InCl3 can catalyze not only o-aminobenzylamine with carbodiimides to afford 2-amino-3,4-dihydroquinazolines, but also o-aminophenol or o-aminothiophenol with carbodiimides to afford 2-aminobenzoxazoles and 2-aminobenzothiazoles, respectively. These reactions all gave good or high yields and better selectivity. Both the stability of the products and the basicity of the eliminated amines play important roles on the chemical selectivity. Moreover, the possible mechanism has been identified.
引文
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[5]Some examples of isocyanate insertion into M-N bond, see:(a) Mao, L. S.; Shen, Q.; Xue, M. Q. "Syntheses of{(MeC5H4)2Ln(THF)[OCN(1Pr)2NPh]}(Ln= Y, Er, Yb) and the X-ray Crystal Structure of the Yttrium Complex:The Active Species for Polymerization of Phenyl Isocyanate by (Diisopropylamido)bis(methylcyclopentadienyl)lanthanides" Organometallics 1997,16,3711-3714. (b) Evans, W. J.; Fujimoto, C. H.; Ziller, J. W. "Organolanthanide-Based Coordination and Insertion Reactivity of the Anion Formed by Deprotonation of s-Caprolactam" Organometallics 2001,20, 4529-4536. (c) Zhou, X. G.; Zhang, L. X.; Zhang, C. M.; Zhang, J.; Zhu, M.; Cai, R. F.; Huang, Z. E.; Huang, Z. X.; Wu, Q. J. "Synthesis, structure and reactivity of tertbutyldimethylsilylcyclopentadienyl lanthanide chlorides, including crystal structures of [(C5H4SiMe2But)2Gd(μ-Cl)]2 and (C5H4SiMe2But)2Er(SBT)(THF)" J. Organomet. Chem.2002,655,120-126. (d) Zhang J.; Cai, R. F.; Weng, L. H.; Zhou, X. G. "Synthesis and Studies on the Reactivities of Dicyclopentadienylytterbium Derivatives Containing Carbazolate and Pyrazolate Ligands" Organometallics 2003,22,5385-5391. (e) Zhang J.; Zhou, X. G.; Cai, R. F.; Weng, L. H. "Reactivity of Organolanthanide and Organolithium Complexes Containing the Guanidinate Ligands toward Isocyanate or Carbodiimide:Synthesis and Crystal Structures" Inorg. Chem.2005,44,716-722. (f) Zhang J.; Cai, R. F.; Chen, Z. X.; Zhou, X. G. "Facile Construction of Lanthanide Metallomacrocycles with the Bridging Imidazolate and Triazolate Ligands and Their Ring Expansions" Inorg. Chem.2007,46,321-327. (g) Wu, Y. J.; Wang, S. W.; Zhu, X. C.; Yang, G. S.; Wei, Y.; Zhang, L. J.; Song, H. B. "Synthesis, Characterization, and Catalytic Activity of Rare Earth Metal Amides Supported by a Diamido Ligand with a CH2SiMe2 Link" Inorg. Chem.2008,47, 5503-5511. (h) Hevia, E.; Perez, J.; Riera, V.; Miguel, D. "Different sites of insertion in the reaction of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] (R=H or Me):N-H vs. Re-N" Chem. Commun.2002,1814-1815. (i) Wang, H.; Wang, Y. R.; Chan, H.-S.; Xie, Z. W. "Synthesis, Structural Characterization, Reactivity, and Thermal Stability of [η5:σ-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)" Inorg. Chem.2006,45,5675-5683. (j) Shen, H.; Chan, H.-S.; Xie, Z. W. "Synthesis, Structure, and Reactivity of [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R= Me, Et)" Organometallics 2007,26,2694-2704. (k) Clulow, A. J.; Selby, J. D.; Cushion, M. G.; Schwarz, A. D.; Mountford, P. "Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands" Inorg. Chem.2008,47,12049-12062. (1) Zhang J.; Han, F. Y.; Han, Y. N.; Chen, Z. X.; Zhou, X. G. "Synthesis and structures of titanium and yttrium complexes with N,N'-tetramethylguanidinate ligands:different reactivity of the M-N bonds toward phenyl isocyanate" Dalton Trans.2009,1806-1811. (m) Shen, H.; Xie, Z. W. "Titanacarborane mediated C-N bond forming/breaking reactions" J. Organomet. Chem.2009,694,1652-1657.
[6]Some examples of isocyanate insertion into M-S bond, see:(a) Shen,O.; Li, H. R.; Yao, C. S.; Yao, Y. M.; Zhang, L. L.;Yu, K. B. "Insertion Reactions of Phenyl Isocyanate and Phenyl Isothiocyanate into the Nd-S Bond of [(CH3C5H4)2Nd(μ-SPh)(THF)]2:Synthesis and Crystal Structures" Organometallics 2001,20,3070-3073. (b) Zhang, J.; Ma, L. P.; Cai, R. F.; Weng, L. H.; Zhou, X. G. "Substituent Effects on Isocyanate Insertion into a Lanthanide-Sulfur Bond. Unexpected Construction of a Coordinated Thiazolate Ring" Organometallics 2005,24,738-742, and references therein.
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D.; Aldridge, S. "Reactivity of Cationic Terminal Borylene Complexes:Novel Mechanisms for Insertion and Metathesis Chemistry Involving Strongly Lewis Acidic Ligand Systems" Organometallics 2009,28,2961-2975. (b) Pothiraja, R.; Milanov, A. P.; Barreca, D.; Gasparotto, A.; Becker, H. W.; Winter, M.; Fischera, R. A.; Devi, A. "Hafnium carbamates and ureates:new class of precursors for low-temperature growth of HfO2 thin films" Chem. Commun.2009,1978-1980.
[4]Some examples of isocyanate insertion into M-C bond, see:(a) Evans, W. J.; Randy N. R.; Joseph, B.-D.; Ziller, J. W. " Synthesis, structure, and reactivity of cyclopentadienyl-free trimethylsilylmethyl yttrium di-tert-butylphenoxide complexes"J. Organomet. Chem.1998,569,89-97. (b) Evans, W. J.; Forrestal, K. J.; Ziller, J. W. "Reaction Chemistry of Sterically Crowded Tris(pentamethylcyclopentadienyl)samarium" J. Am. Chem. Soc.1998,120, 9273-9282. (c) Zhou, X. G.; Zhang, L. B.; Zhu, M.; Cai, R. F.; Weng, L. H. "Insertion Reaction of Phenyl Isocyanate into the Ln-C σ-Bond of Organolanthanide Complexes:Synthesis, Characterization, and Crystal Structures of{(C5H4CH3)2Ln[μ-η1:η3-OC(R)NPh]}2 (Ln= Sm, Dy, Er, Ho; R=n-butyl, a-naphthyl)" Organometallics 2001,20,5700-5706. (d) Kuninobu, Y.; Tokunaga, Y.; Kawata, A.; Takai, K. "Insertion of Polar and Nonpolar Unsaturated Molecules into Carbon-Rhenium Bonds Generated by C-H Bond Activation: Synthesis of Phthalimidine and Indene Derivatives" J. Am. Chem. Soc.2006,128, 202-209. (e) Sanchez-Nieves, J.; Royo, P.; Mosquera, M. E. G. "Synthesis of the Cation Complex [TaCp*Me3]+ and a Comparison of Its Reactivity with That of [TaCp*Me4]" Organometallics 2006,25,2331-2336. (f) Antinolo, A.; Fernandez-Galan, R.; Molina, N.; Otero, A.; Rivilla, I.; Rodriguez, A. M. "New alkenyl-substituted group 4 C-ansa-metallocene complexes. Reactivity of the substituent at the carbon ansa bridge" J. Organomet. Chem.2009,694, 1959-1970.
[5]Some examples of isocyanate insertion into M-N bond, see:(a) Mao, L. S.; Shen, Q.; Xue, M. Q. "Syntheses of{(MeC5H4)2Ln(THF)[OCN(1Pr)2NPh]}(Ln= Y, Er, Yb) and the X-ray Crystal Structure of the Yttrium Complex:The Active Species for Polymerization of Phenyl Isocyanate by (Diisopropylamido)bis(methylcyclopentadienyl)lanthanides" Organometallics 1997,16,3711-3714. (b) Evans, W. J.; Fujimoto, C. H.; Ziller, J. W. "Organolanthanide-Based Coordination and Insertion Reactivity of the Anion Formed by Deprotonation of s-Caprolactam" Organometallics 2001,20, 4529-4536. (c) Zhou, X. G.; Zhang, L. X.; Zhang, C. M.; Zhang, J.; Zhu, M.; Cai, R. F.; Huang, Z. E.; Huang, Z. X.; Wu, Q. J. "Synthesis, structure and reactivity of tertbutyldimethylsilylcyclopentadienyl lanthanide chlorides, including crystal structures of [(C5H4SiMe2But)2Gd(μ-Cl)]2 and (C5H4SiMe2But)2Er(SBT)(THF)" J. Organomet. Chem.2002,655,120-126. (d) Zhang J.; Cai, R. F.; Weng, L. H.; Zhou, X. G. "Synthesis and Studies on the Reactivities of Dicyclopentadienylytterbium Derivatives Containing Carbazolate and Pyrazolate Ligands" Organometallics 2003,22,5385-5391. (e) Zhang J.; Zhou, X. G.; Cai, R. F.; Weng, L. H. "Reactivity of Organolanthanide and Organolithium Complexes Containing the Guanidinate Ligands toward Isocyanate or Carbodiimide:Synthesis and Crystal Structures" Inorg. Chem.2005,44,716-722. (f) Zhang J.; Cai, R. F.; Chen, Z. X.; Zhou, X. G. "Facile Construction of Lanthanide Metallomacrocycles with the Bridging Imidazolate and Triazolate Ligands and Their Ring Expansions" Inorg. Chem.2007,46,321-327. (g) Wu, Y. J.; Wang, S. W.; Zhu, X. C.; Yang, G. S.; Wei, Y.; Zhang, L. J.; Song, H. B. "Synthesis, Characterization, and Catalytic Activity of Rare Earth Metal Amides Supported by a Diamido Ligand with a CH2SiMe2 Link" Inorg. Chem.2008,47, 5503-5511. (h) Hevia, E.; Perez, J.; Riera, V.; Miguel, D. "Different sites of insertion in the reaction of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] (R=H or Me):N-H vs. Re-N" Chem. Commun.2002,1814-1815. (i) Wang, H.; Wang, Y. R.; Chan, H.-S.; Xie, Z. W. "Synthesis, Structural Characterization, Reactivity, and Thermal Stability of [η5:σ-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)" Inorg. Chem.2006,45,5675-5683. (j) Shen, H.; Chan, H.-S.; Xie, Z. W. "Synthesis, Structure, and Reactivity of [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R= Me, Et)" Organometallics 2007,26,2694-2704. (k) Clulow, A. J.; Selby, J. D.; Cushion, M. G.; Schwarz, A. D.; Mountford, P. "Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands" Inorg. Chem.2008,47,12049-12062. (1) Zhang J.; Han, F. Y.; Han, Y. N.; Chen, Z. X.; Zhou, X. G. "Synthesis and structures of titanium and yttrium complexes with N,N'-tetramethylguanidinate ligands:different reactivity of the M-N bonds toward phenyl isocyanate" Dalton Trans.2009,1806-1811. (m) Shen, H.; Xie, Z. W. "Titanacarborane mediated C-N bond forming/breaking reactions" J. Organomet. Chem.2009,694,1652-1657.
[6]Some examples of isocyanate insertion into M-S bond, see:(a) Shen,O.; Li, H. R.; Yao, C. S.; Yao, Y. M.; Zhang, L. L.;Yu, K. B. "Insertion Reactions of Phenyl Isocyanate and Phenyl Isothiocyanate into the Nd-S Bond of [(CH3C5H4)2Nd(μ-SPh)(THF)]2:Synthesis and Crystal Structures" Organometallics 2001,20,3070-3073. (b) Zhang, J.; Ma, L. P.; Cai, R. F.; Weng, L. H.; Zhou, X. G. "Substituent Effects on Isocyanate Insertion into a Lanthanide-Sulfur Bond. Unexpected Construction of a Coordinated Thiazolate Ring" Organometallics 2005,24,738-742, and references therein.
[7]Some examples of isocyanate insertion into M-O bond, see:(a) Zhang, C. M.; Liu, R. T.; Zhang, J.; Chen, Z. X.; Zhou, X. G. "Reactivity of Lanthanocene Hydroxides toward Ketene, Isocyanate, Lanthanocene Alkyl, and Triscyclopentadienyllanthanide Complexes" Inorg. Chem.2006,45,5867-5877. (b) Ghosh, R.; Nethaji, M.; Samuelson, A. G. "Reversible double insertion of aryl isocyanates into the Ti-O bond of titanium(Ⅳ) isopropoxide" J. Organomet. Chem.2005,690,1282-1293. (c) Campora, J.; Matas, I.; Palma, P.; Alvarez, E.; Graiff, C.; Tiripicchio, A. "Monomeric Alkoxo and Amido Methylnickel(Ⅱ) Complexes. Synthesis and Heterocumulene Insertion Chemistry" Organometallics 2007,26,3840-3849. (d) Hevia, E.; Perez, J.; Riera, L.; Riera, V.; delRio, I.; Garcia-Granda, S.; Miguel, D. "Insertion of Unsaturated Organic Electrophiles into Molybdenum-Alkoxide and Rhenium_Alkoxide Bonds of Neutral, Stable Carbonyl Complexes" Chem. Eur. J.2002,8,4510-4521. (e) Cuesta, L.; Gerbino, D. C.; Hevia, E.; Morales, D.; Clemente, M. E. N.; Perez, J.; Riera, L.; Riera, V.; Miguel, D.; del Rio, I.; Garcia-Granda, S. "Reactivity of Molybdenum and Rhenium Hydroxo-Carbonyl Complexes toward Organic Electrophiles" Chem. Eur. J.2004,10,1765-1777. (f) Cuesta, L.; Huertos, M. A.; Morales, D.; Perez, J,; Riera, L.; Riera, V.; Miguel, D.; Menendez-Velazquez, A.; Garcia-Granda, S. "Synthesis, Structure, and Reactivity of Mononuclear Re(Ⅰ) Oximato Complexes" Inorg. Chem.2007,46,2836-2845. (g) Ruiz, J.; Marti'nez, M. T.; Florenciano, F.; Rodriguez, V.; Lopez, G. "Insertion Reactions into Pd-O and Pd-N Bonds:Preparation of Alkoxycarbonyl, Carbonato, Carbamato, Thiocarbamate, and Thioureide Complexes of Palladium(Ⅱ)" Inorg. Chem.2003, 42,3650-3661. (h) Kumar, A.; De, S.; Samuelson, A. G.; Jemmis, E. D. "Differing Reactivities of Zirconium and Titanium Alkoxides with Phenyl Isocyanate:An Experimental and Computational Study" Organometallics 2008, 27,955-960.
[8]Some examples of isocyanate insertion into M-H bond, see:(a) Jetz, W.; Angelici, R. J. "Carboxamido Complexes of Molybdenum and Tungsten. Alkyl Isocyanate Insertion into a Tungsten-Hydrogen Bond" J. Am. Chem. Soc.1972, 94,3799-3802. (b) Field, L. D.; Shaw, W. J.; Turner, P. "Addition of Nitrogen-Containing Heteroallenes to Iron(Ⅱ)-Hydrides" Organometallics 2001, 20,3491-3499. (c) Albertin, G.; Antoniutti, S.; Roveda, G. "Insertion of heteroallenes into the rhenium-hydride bond" Inorg. Chim. Acta 2005,358, 3093-3105. (d) Tardif, O.; Hashizume, D.; Hou, Z. M. "Hydrogenation of Carbon Dioxide and Aryl Isocyanates by a Tetranuclear Tetrahydrido Yttrium Complex. Isolation, Structures, and CO2 Insertion Reactions of Methylene Diolate and μ3-Oxo Yttrium Complexes" J. Am. Chem. Soc.2004,126,8080-8081.
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