Syntheses of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands and their catalytic activity toward the hydrophosphonylation reaction of aldehydes and ketones

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• 作者：Kun Nie ; Chengwei Liu ; Yong Zhang ; Yingming Yao
• 关键词：bimetallic lanthanide complex ; bridged bis(guanidinate) ligand ; hydrophosphonylation reaction ; aldehyde ; ketone
• 刊名：SCIENCE CHINA Chemistry
• 出版年：2015
• 出版时间：September 2015
• 年：2015
• 卷：58
• 期：9
• 页码：1451-1460
• 全文大小：919 KB
• 参考文献：1 a).Edelmann FT. Lanthanide amidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare-earth oxide thin films. Chem Soc Rev, 2009, 38: 2253-268CrossRef
  1 b).Edelmann FT. Lanthanide amidinates and guanidinates in catalysis and materials science: a continuing success story. Chem Soc Rev, 2012, 41: 7657-672CrossRef
  2 a).Trifonov AA, Skvortsov GG, Lyubov DM, Skorodumova NA, Fukin GK, Baranov EV, Glushakova VN. Postmetallocene lanthanide-hydrido chemistry: a new family of complexes [{Ln{(Me3Si)2-NC(NiPr)2}2(μ-H)}2] (Ln=Y, Nd, Sm, Gd, Yb) supported by guanidinate ligands-synthesis, structure, and catalytic activity in olefin polymerization. Chem Eur J, 2006, 12: 5320-327CrossRef
  2 b).Lyubov DM, Fukin GK, Trifonov AA. N,N-diisopropyl-N-bis(trimethylsilyl) guanidinate ligand as a supporting coordination environment in yttrium chemistry. Synthesis, structure, and properties of complexes [(Me3Si)2NC(Ni-Pr)2]YCl2(THF)2, [(Me3Si)2NC(Ni-Pr)2]Y(CH2Si-Me3)2(THF)2, and [(Me3Si)2NC(Ni-Pr)2]Y[(μ-H)(μ-Et)2BEt]2(THF). Inorg Chem, 2007, 46: 11450-1456CrossRef
  3 a).Cui P, Chen Y, Li G, Xia W. An ansa-heteroborabenzene divalent lanthanide amide through C-H bond cleavage. Angew Chem Int Ed, 2008, 47: 9944-947CrossRef
  3 b).Lu Z, Yap GPA, Richeson DS. Tetrasubstituted guanidinate anions as supporting ligands in organoyttrium chemistry. Organometallics, 2001, 20: 706-12CrossRef
  3 c).Trifonov AA, Lyubov DM, Fukin GK, Baranov EV, Kurskii YA. Alkylyttrium complexes supported by N,N-dicyclohexyl-N-bis(trimethylsilyl) guanidinate ligands. Organometallics, 2006, 25: 3935-942CrossRef
  3 d).Ge S, Meetsma A, Hessen B. Highly efficient hydrosilylation of alkenes by organoyttrium catalysts with sterically demanding amidinate and guanidinate ligands. Organometallics, 2008, 27: 3131-135CrossRef
  3 e).Luo Y, Yao Y, Shen Q. [(SiMe3)2NC(NiPr)2]2Ln(μ-Me)2Li(TMEDA) (Ln=Nd, Yb) as effective single-component initiators for styrene polymerization. Macromolecules, 2002, 35: 8670-671CrossRef
  3 f).Luo Y, Yao Y, Shen Q, Yu K, Weng L. Synthesis and characterization of lanthanide(III) bis(guanidinate) derivatives and the catalytic activity of methyllanthanide bis(guanidinate) complexes for the polymerization of ?-caprolactone and methyl methacrylate. Eur J Inorg Chem, 2003: 318-23
  3 g).Trifonov AA, Lyubov DM, Fedorova EA, Fukin GK, Schumann H, Mühle S, Hummert M, Bochkarev MN. Chloro, alkyl and aryl complexes of rare earth metals supported by bulky tetrasubstituted guanidinate ligands. Eur J Inorg Chem, 2006: 747-56
  3 h).Zhang J, Zhou X, Cai R, Weng L. Reactivity of organolanthanide and organolithium complexes containing the guanidinate ligands toward isocyanate or carbodiimide: synthesis and crystal structures. Inorg Chem, 2005, 44: 716-22CrossRef
  3 i).Zhang Z, Zhang L, Li Y, Hong L, Chen Z, Zhou X. Activation of bis(guanidinate)lantha-nide alkyl and aryl complexes on elemental sulfur: synthesis and characterization of bis(guanidinate)lanthanide thiolates and disulfides. Inorg Chem, 2010, 49: 5715-722CrossRef
  4 a).Yao Y, Luo Y, Chen J, Zhang Z, Zhang Y, Shen Q. Synthesis and characterization of bis(guanidinate)lanthanide diisopropylamido complexes: new highly active initiators for the polymerizations of ?-caprolactone and methyl methacrylate. J Organomet Chem, 2003, 679: 229-37CrossRef
  4 b).Giesbrecht GR, Whitener GD, Arnold J. Monoguanidinate complexes of lanthanum: synthesis, structure and their use in lactide polymerization. J Chem Soc, Dalton Trans, 2001: 923-27
  4 c).Wang Y, Luo Y, Chen J, Xue H, Liang H. Synthesis of mono(guanidinate) rare earth metal bis(amide) complexes and their performance in the ring-opening polymerization of L-lactide and rac-lactide. New J Chem, 2012, 36: 933-40CrossRef
  5.Ajellal N, Lyubov DM, Sinenkov MA, Fukin GK, Cherkasov AV, Thomas CM, Carpentier JF, Trifonov AA. Bis(guanidinate) alkoxide complexes of lanthanides: synthesis, structures and use in immortal and stereoselective ring-opening polymerization of cyclic esters. Chem Eur J, 2008, 14: 5440-448CrossRef
  6.Cao Y, Du Z, Li W, Li J, Zhang Y, Xu F, Shen Q. Activation of carbodiimide and transformation with amine to guanidinate group by Ln(OAr)3(THF)2 (Ln: lanthanide and yttrium) and Ln(OAr)3(THF)2 as a novel precatalyst for addition of amines to carbodiimides: influence of aryloxide group. Inorg Chem, 2011, 50: 3729-737CrossRef
  7 a).Qian C, Zhang X, Li J, Xu F, Zhang Y, Shen Q. Trisguanidinate lanthanide complexes: syntheses, structures, and catalytic activity for mild amidation of aldehydes with amines. Organometallics, 2009, 28: 3856-862CrossRef
  7 b).Zhang X, Wang C, Qian C, Han F, Xu F, Shen Q. Heterobimetallic dianionic guanidinate complexes of lanthanide and lithium: highly efficient precatalysts for catalytic addition of amines to carbodiimides to synthesize guanidines. Tetrahedron, 2011, 67: 8790-799CrossRef
  8 a).
• 作者单位：Kun Nie (1) (2)
  Chengwei Liu (2)
  Yong Zhang (2)
  Yingming Yao (2)
  
  1. School of Chemistry and Chemical Engineering, Taishan University, Taian, 271021, China
  2. Key Laboratory of Organic Synthesis of Jiangsu Province; College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Chinese Library of Science
  Chemistry
  
• 出版者：Science China Press, co-published with Springer
• ISSN：1869-1870

文摘

A series of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands {[(Me₃Si)₂N]₂Ln[(RN)₂-CN(CH₂)₂]}₂ [R= i Pr, Ln=Sm (1), Yb (2), Y (3); R=cyclohexyl (Cy), Ln=Sm (4), and Yb (5)] were synthesized through the metathesis reactions of {Ln(μ-Cl)[N(SiMe₃)₂]₂(THF)}₂ (Ln=Sm, Yb, Y) with lithium guanidinate {Li[(RN)₂CN(CH₂)₂]}₂ (R= i Pr, Cy), the latter of which was generated in situ by the reaction of carbodiimides with lithium amides. Complexes 1-strong class="EmphasisTypeBold ">5 were well characterized by elemental analyses, IR spectra, and (for Complex 3) NMR spectroscopy. The solid-state molecular structures of all of the complexes were determined by single-crystal X-ray analyses with the exception of Complex 3, which showed similar unsolvated centrosymmetric dinuclear structures. Each of the lanthanide centers is four-coordinated with two nitrogen atoms from a guanidinate ligand and two nitrogen atoms from two amido groups. The piperazidine rings adopt chair conformations in all cases. These organolanthanide complexes were found to be efficient catalysts for the hydrophosphonylation reaction of various aldehydes and unactivated ketones and to afford α-hydroxyphosphonates in high yields under low catalyst loading (0.1 mol%) in a short reaction time. Keywords bimetallic lanthanide complex bridged bis(guanidinate) ligand hydrophosphonylation reaction aldehyde ketone