由阴离子型氮杂环卡宾支撑的异双金属硬币金属-钌配合物
Heterobimetallic Coinage Metal-Ruthenium Complexes Supported by Anionic N-Heterocyclic Carbenes.
作者信息
Planer Sebastian, Frosch Jenni, Koneczny Marvin, Trzybiński Damian, Woźniak Krzysztof, Grela Karol, Tamm Matthias
机构信息
Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089, Warsaw, Poland.
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.
出版信息
Chemistry. 2021 Nov 2;27(61):15217-15225. doi: 10.1002/chem.202102553. Epub 2021 Sep 3.
The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating borate moiety (WCA-NHC, WCA=B(C F ) , NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were used for the preparation of silver(I) or copper(I) WCA-NHC complexes. While the reactions in THF with AgCl or CuCl afforded anionic mono- and dicarbene complexes with solvated lithium counterions [Li(THF) ] (n=3, 4), the reactions in toluene proceeded with elimination of LiCl and formation of the neutral phosphine and arene complexes [(WCA-NHC)M(PPh )] and [(WCA-NHC)M(η -toluene)] (M=Ag, Cu). The latter were used for the preparation of chlorido- and iodido-bridged heterobimetallic Ag/Ru and Cu/Ru complexes [(WCA-NHC)M(μ-X) Ru(PPh )(η -p-cymene)] (M=Ag, Cu, X=Cl; M=Ag, X=I). Surprisingly, these complexes resisted the elimination of CuCl, AgCl, or AgI, precluding WCA-NHC transmetalation.
含弱配位硼酸根部分的阴离子型氮杂环卡宾的锂配合物[(WCA-NHC)Li(甲苯)]（WCA-NHC中，WCA = B(C₆F₅)₄，NHC = IDipp = 1,3-双(2,6-二异丙基苯基)咪唑啉-2-亚基）用于制备银(I)或铜(I)的WCA-NHC配合物。虽然在四氢呋喃中与AgCl或CuCl的反应得到了带有溶剂化锂抗衡离子[Li(THF)ₙ]（n = 3, 4）的阴离子型单卡宾和双卡宾配合物，但在甲苯中的反应则伴随着LiCl的消除，并形成中性膦和芳烃配合物[(WCA-NHC)M(PPh₃)]和[(WCA-NHC)M(η⁶-甲苯)]（M = Ag, Cu）。后者用于制备氯桥连和碘桥连的异双金属Ag/Ru和Cu/Ru配合物[(WCA-NHC)M(μ-X)Ru(PPh₃)(η⁶-p-异丙基苯)]（M = Ag, Cu, X = Cl；M = Ag, X = I）。令人惊讶的是，这些配合物能阻止CuCl、AgCl或AgI的消除，从而排除了WCA-NHC的金属转移反应。
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