Novel nucleophilic reactivity of disulfido ligands coordinated parallel to M-M (M = Rh, Ir) bonds

被引：22

作者：

Nishioka, T ^{[1
]}

Kitayama, H

Breedlove, BK

Shiomi, K

Kinoshita, I

Isobe, K

机构：

[1] Osaka City Univ, Grad Sch Sci, Dept Mat Sci, Sumiyoshi Ku, Osaka 5588585, Japan

[2] Kanazawa Univ, Fac Sci, Dept Chem, Kanazawa, Ishikawa 9201192, Japan

[3] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 18期

关键词：

D O I：

10.1021/ic049855t

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of trans-[(MCp*)(2)(mu-CH2)(2)Cl-2] (M = Rh, Ir; Cp* = eta(5)-C5Me5) with Li2S2 afforded the disulfido complexes [(MCp*)(2)(mu-CH2)(2)(mu-S-2-S:S')] which were easily oxidized by 02 to give the oxygenated complexes [(MCP*)(2)(mu-CH2)(2)(mu-SSO2-S:S')]. Although [(RhCP*)(2)(mu-CH2)(2)(mu-S-2-S:S')] gave a complicated mixture when reacted with CH2Cl2 or CHCl3, [(IrCP*)(2)(mu-CH2)(2)(mu-S-2-S:S')] reacted with both CH2Cl2 and CHCl3 to give the dithioformato complex [(IrCP*)(2)(mu-CH2)(2)(mu-S2CH-S:S')]Cl and the cyclotetrasulfido complex [{(IrCp*)(2)(mu-CH2)(2)}(2)(mu-S-4-S:S':S":S'")]Cl-2. The oxygenated complexes [(RhCP*)(2)(mu-CH2)(2)(mu-SSO2-S:S')] reacted with hydrocarbyl halides to afford bridging hydrocarbyl thiolato complexes accompanied by the generation of SO2 gas. These complexes have been characterized by NMR spectroscopy, ESI-MS, and X-ray diffraction.

引用

页码：5688 / 5697

页数：10

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