Preparation and C-N cleavage reactions of bis[(dimethylphosphino)ethane]ruthenium isocyanide complexes

Article abstract of DOI:10.1021/om00140a012

The thermal reaction of (DMPE)₂Ru(naphthyl)H [DMPE = bis(dimethylphosphino)ethane] with isocyanides is described. Thermolysis in the presence of excess neopentyl isocyanide at 60°C in benzene solution results in the formation of the simple substitution complex (DMPE)₂Ru(CNCH₂CMe₃) plus naphthalene. Thermolysis in the presence of excess phenyl isocyanide results in the formation of the unusual monodentate DMPE complex Ru(η²-DMPE)(η¹-DMPE)(CNPh)₂. Continued heating ultimately forms Ru(DMPE)₂(CNPh) plus phenyl isocyanide polymer. Thermolysis with ethyl isocyanide leads to the formation of Ru(DMPE)₂(CNEt). Thermolysis in the presence of tert-butyl isocyanide produces two organometallic products, Ru(DMPE)₂(CN)₂ and Ru(DMPE)₂(CN)H, plus four organic products, trimethylacetonitrile, naphthalene, isobutylene, and isobutane, A mechanism is suggested for the formation of these rearrangement and C-N bond cleavage products. The dicyanide molecule Ru(DMPE)₂(CN)₂ was found to crystallize in the orthorhombic space group Pccn with a = 9.2842 (14) A?, b = 14.1091 (30) A?, c = 16.3641 (50) A?, V = 2143.6 (1.4) A?³, and Z = 4.