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

• Published in: Organometallics Vol. 25; no. 3; pp. 560 - 562
• Main Authors: Arashiba, Kazuya, Matsukawa, Shoji, Kuwata, Shigeki, Tanabe, Yoshiaki, Iwasaki, Masakazu, Ishii, Youichi
• Format: Journal Article
• Language: English
• Published: American Chemical Society 30.01.2006
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om0510573

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 +).