三配位镍卡宾配合物[1,2-双（二叔丁基膦基）乙烷]Ni=CPh(2)的合成、结构及反应
Synthesis, structure, and reactions of a three-coordinate nickel-carbene complex, [1,2-Bis(di-tert-butylphosphino)ethane]Ni=CPh(2).
作者信息
Mindiola Daniel J, Hillhouse Gregory L
机构信息
Searle Chemistry Laboratory, Department of Chemistry, The University of Chicago, Illinois 60637, USA.
出版信息
J Am Chem Soc. 2002 Aug 28;124(34):9976-7. doi: 10.1021/ja0269183.
The three-coordinate nickel-carbene complex (dtbpe)Ni=CPh2 (3) was prepared from the thermolysis of the diphenyldiazoalkane complex (dtbpe)Ni(N,N':eta2-N2CPh2) (2) (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane). Complex 3 was structurally characterized by single-crystal X-ray diffraction methods (Ni-C = 1.836(2) A). Complex 3 reacts with 2 equiv of CO2 to afford (dtbpe)Ni{OC(O)CPh2C(O)O} (4), with diphenylketene to give (dtbpe)Ni{OC(=CPh2)CPh2} (5), with excess CO to transfer the carbene fragment and generate diphenylketene and (dtbpe)Ni(CO)2 (6), with sulfur dioxide to give the metallasulfone (dtbpe)Ni{C,S:eta2-S(O)2CPh2} (7), and with the Brønsted acid [HNMe2Ph][B(C6F5)4] to give the alkyl cation [(dtbpe)Ni(CHPh2)][B(C6F5)4] (8). Complexes 4, 5, and 7 have also been characterized by single-crystal X-ray diffraction methods.
三配位镍-卡宾配合物(dtbpe)Ni=CPh₂(3)由二苯基重氮烷配合物(dtbpe)Ni(N,N':η²-N₂CPh₂)(2)(dtbpe = 1,2-双(二叔丁基膦基)乙烷)热解制备。配合物3通过单晶X射线衍射方法进行结构表征(Ni-C = 1.836(2) Å)。配合物3与2当量的CO₂反应生成(dtbpe)Ni{OC(O)CPh₂C(O)O}(4)，与二苯基乙烯酮反应生成(dtbpe)Ni{OC(=CPh₂)CPh₂}(5)，与过量的CO反应转移卡宾片段并生成二苯基乙烯酮和(dtbpe)Ni(CO)₂(6)，与二氧化硫反应生成金属砜(dtbpe)Ni{C,S:η²-S(O)₂CPh₂}(7)以及与布朗斯特酸[HNMe₂Ph][B(C₆F₅)₄]反应生成烷基阳离子[(dtbpe)Ni(CHPh₂)]B(C₆F₅)₄。配合物4、5和7也通过单晶X射线衍射方法进行了表征
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