Synthesis, Structure, and Reactions of a Three-Coordinate Nickel-Carbene Complex, {1,2-Bis(di-tert-butylphosphino)ethane}NiCPh2
- 1 August 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (34) , 9976-9977
- https://doi.org/10.1021/ja0269183
Abstract
The three-coordinate nickel-carbene complex (dtbpe)NiCPh2 (3) was prepared from the thermolysis of the diphenyldiazoalkane complex (dtbpe)Ni(N,N‘:η2-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) Å). 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:η2-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.Keywords
This publication has 21 references indexed in Scilit:
- X-ray Crystallographic and Theoretical Comparison of Ge[2,4,6-(CF3)3C6H2]2and Ge[N(SiMe3)2]2as Ligands in (Ph3P)2NiGeX2ComplexesOrganometallics, 1999
- Isolation and Characterization of Neutral Platinum Silylene Complexes of the Type (R3P)2PtSiMes2(Mes = 2,4,6-Trimethylphenyl)Journal of the American Chemical Society, 1998
- C−H Activation at Cationic Platinum(II) CentersJournal of the American Chemical Society, 1997
- Lewis Acid-Catalyzed Synthesis of AziridinesThe Journal of Organic Chemistry, 1996
- A Palladium-Catalyzed Stannole SynthesisJournal of the American Chemical Society, 1996
- .eta.2-(C,O) Ketene coordination at nickel(O). Synthesis, bonding, and molecular structure of (dtbpm)Ni[.eta.2-(C,O)-Ph2C2O] [dtbpm = bis(di-tert-butylphosphino)methane]Organometallics, 1992
- Carbene Complexes in Organic Synthesis [New Synthetic Methods (47)]Angewandte Chemie International Edition in English, 1984
- Alkylidene complexes of niobium and tantalumAccounts of Chemical Research, 1979
- Compounds containing platinum–carbon bonds. Part IV. Crystal and molecular structures of trans- and cis-dichloro(l,3-diphenylimidazol-idin-2-ylidene)(triethylphosphine)platinum(II)J. Chem. Soc., Dalton Trans., 1974
- On the Existence of a Tungsten Carbonyl Carbene ComplexAngewandte Chemie International Edition in English, 1964