Electrophilic O-methylation of a terminal nitrosyl ligand attained by an early-late heterobimetallic effect

被引：22

作者：

Arashiba, K

Matsukawa, S

Kuwata, S

Tanabe, Y

Iwasaki, M

Ishii, Y ^{[1
]}

机构：

[1] Chuo Univ, Fac Sci & Engn, Dept Appl Chem, Bunkyo Ku, Tokyo 1128551, Japan

[2] Univ Tokyo, Inst Ind Sci, Meguro Ku, Tokyo 1538505, Japan

[3] Tokyo Inst Technol, Dept Appl Chem, Grad Sch Sci & Engn, Meguro Ku, Tokyo 1528552, Japan

[4] Saitama Inst Technol, Fac Engn, Dept Appl Chem, Okabe, Saitama 3690293, Japan

[5] Inst Mol Sci, Coordinat Chem Labs, Okazaki, Aichi 4448787, Japan

来源：

ORGANOMETALLICS | 2006年 / 25卷 / 03期

关键词：

D O I：

10.1021/om0510573

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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'Cl-2(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)(mu-S)(2)M'(NO)Cp*] (M = Rh, Ir; V = 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)(mu-S)(2)W(NOMe)Cp*](+) (9(+)), while methylation of the Rh-Mo complex 5 results in S-methylation, giving the methanethiolato complex [Cp*Rh(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*](+) (10(+)).

引用

页码：560 / 562

页数：3

共 30 条

[1] LIGAND-TRANSFORMATION SYNTHESES AND STEREOPHYSICAL INVESTIGATIONS OF 48-ELECTRON MIXED CP-CP' TRIANGULAR MNFE2 CLUSTERS CONTAINING MNFE2(MU-2-CO)2(MU-2-NO)(MU-3-NX) CORES (WHERE X=O, OH, OME, H) - STRUCTURAL-BONDING CONSEQUENCES DUE TO CONVERSIONS OF A CAPPING NITROSYL (MU-3-NO) LIGAND INTO ELECTRONICALLY EQUIVALENT (MU-3-NOR)+ LIGANDS (R=H, ME) AND INTO AN IMIDO (MU-3-NH)+ LIGAND AND TO THE ONE-ELECTRON REDUCTION OF AN IMIDO-CAPPED MNFE2 CLUSTER [J].