Carbene and silylene complexes of nickel supported by a chelating bisphosphine ligand

INOR 124

Vlad M. Iluc, gh15@uchicago.edu and Gregory L. Hillhouse, g-hillhouse@uchicago.edu. Department of Chemistry, University of Chicago, 5735 S. Ellis Ave., Chicago, IL 60637
The coordination environment provided by the (dtbpe)NiL platform (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) allows isolation of various carbene and silylene complexes of the type (dtbpe)Ni=CR2 and (dtbpe)Ni(H)(SiR2). The structures of these complexes were investigated in solution by NMR spectroscopy and in the solid-state by single-crystal X-ray diffraction. The nature of the Ni=E (E = CR2, SiR2) bond was also addressed through DFT calculations. A bulky terphenyl substituent on the carbene ligand in the complex (dtbpe)Ni=CH( 2,6-dimesitylphenyl) was used in order to target higher-oxidation state nickel carbenes.