OXIDATIVE-ADDITION REACTIONS OF M(CO)4(N-N) (M=Mo or W) USING IODOBENZENE DICHLORIDE. ISOLATION OF SEVEN-COORDINATE CATIONS OF MOLYBDENUM(II) AND TUNGSTEN(II) CONTAINING ALKYL ISOCYANIDE AND BIDENTATE N-HETEROCYCLE LIGANDS

Article abstract of DOI:10.1016/0022-328X(84)85038-X

A series of seven coordinate tungsten(II) salts (PF6)2 (R = CHMe2, CMe3, C6H11, or CH2Ph; N-N = bipy, Me2bipy, or phen) have been prepared in high yield (> 75percent).The synthetic procedure involves the oxidation of the metal carbonyl derivative W(CO)4(N-N) with iodobenzene dichloride, followed by displacement of carbon monoxide and chloride ligands from the intermediate W(CO)3(N-N)Cl2 by alkyl isocyanide.These reactions work equally well for the conversion of Mo(CO)4(N-N) to (PF6)2.The dealkylation of (PF6)2 to give <2(μCN)>(PF6)3 occurs in refluxing ethanol.The direct reaction of (PF6)2 with N-N in refluxing 1-propanol leads to the dealkylation product PF6, but there is no evidence for the substitution of the Me3CNC ligands by N-N via such a route.