Synthesis, structure, and reactions of a three-coordinate nickel-carbene complex, [1,2-Bis(di-tert-butylphosphino)ethane]Ni=CPh(2).
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.
Searle Chemistry Laboratory, Department of Chemistry, The University of Chicago, Illinois 60637, USA.
Daniel J
DJ
Mindiola
Gregory L
GL
Hillhouse
D006838:Hydrocarbons; D009682:Magnetic Resonance Spectroscopy; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014961:X-Ray Diffraction
D006838:Hydrocarbons; D009942:Organometallic Compounds; C030011:carbene; D009532:Nickel; D008697:Methane