Noninnocent behavior of ancillary ligands: apparent trans coupling of a saturated N-heterocyclic carbene unit with an ethyl ligand mediated by nickel.

Journal article

Oxidative addition of the tridentate N-heterocyclic carbene (NHC) diphosphine ligand precursor ([PCP]H)PF(6) (1) {[PCP] = o-(i)Pr(2)PC(6)H(4)(NC(3)H(4)N)o-C(6)H(4)P(i)Pr(2)} to Ni(COD)(2) results in the formation of the nickel(II) hydride complex ([PCP]NiH)PF(6) (2). This hydride undergoes a rapid reaction with ethylene to generate a nickel(0) complex in which an ethyl group has been transferred to the carbene carbon of the original NHC-diphosphine ligand. If the first intermediate is the anticipated square-planar nickel(II) ethyl species, then the formation of the product would require a process that involves a trans C-C coupling of the NHC carbon and a presumed Ni-ethyl intermediate. Deuterium-labeling studies provide evidence for migratory insertion of the added ethylene into the Ni-H bond rather than into the Ni-carbene linkage; this is based on the observed deuterium scrambling, which requires reversible beta-elimination, alkene rotation, and hydride readdition. However, density functional theory studies suggest that a key intermediate is an agostic ethyl species that has the Ni-C bond cis to the NHC unit. A possible transition state containing two cis-disposed carbon moieties was also identified. Such a process represents a new pathway for catalyst deactivation involving NHC-based metal complexes.

Authors: Steinke, T; Shaw, B; Jong, H; Patrick, B; Fryzuk, MD

• Publication status: Published
• Journal: Journal of the American Chemical Society
• Volume: 131
• Issue: 30
• Pages: 10461-10466
• Publication date: 2009-08-01
• DOI: 10.1021/ja901346g
• EISSN: 1520-5126
• ISSN: 0002-7863
• Language: English