Electrophilic O-Methylation of a Terminal Nitrosyl Ligand Attained by an Early−Late Heterobimetallic Effect

The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)2(PMe3)] (M = Rh, Ir) with the group 6
nitrosyl complexes [Cp*M‘Cl2(NO)] (M‘ = Mo, W) in the
presence of NEt3 affords a series of the bis(sulfido)-bridged
early−late heterobimetallic (ELHB) complexes [Cp*M(PMe3)(μ-S)2M‘(NO)Cp*] (M = Rh, Ir; M‘ = Mo, W). Upon treatment
of the Rh−W complex 7 with MeOTf, the oxygen atom of the
terminal nitrosyl ligand is readily methylated to form the
methoxyimido complex [Cp*Rh(PMe3)(μ-S)2W(NOMe)Cp*]+
(9+), while methylation of the Rh−Mo complex 5 results in
S-methylation, giving the methanethiolato complex [Cp*Rh(PMe3)(μ-SMe)(μ-S)Mo(NO)Cp*]+ (10+).