Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes.

The generation of diphosphorus molecules P2 under mild conditions in solution is a useful strategy to generate diphosphines via [4+2] cycloadditions. We recently described the release of P2 units from the nickel butterfly complex [{(IMes)Ni(CO)}2(μ2,η2:η2‐P2)] (IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes. In addition to formation of P4 (the dimerisation product of P2), the reactions afford nickel complexes of novel pincer‐type ligands. Aryl isothiocyanates undergo a trimerisation within the coordination sphere of nickel and afford square planar nickel complexes with S−C−S pincer‐ligand frameworks. Carbon disulfide coordinates to the [(IMes)Ni]‐fragment in an η2‐fashion, affording a dinuclear complex. Similar products are formed when the N‐heterocyclic carbene nickel(0) complex [(IMes)Ni(vtms)2] is used as a precursor (vtms=vinyltrimethylsilane). [ABSTRACT FROM AUTHOR]