Issue 8, 2010
From the journal:

Dalton Transactions

Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity†‡

Xian-Kuan Huo,a   Ge Sua  and  Guo-Xin Jin*a  

* Corresponding authors

a Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Advanced Materials Laboratory, Fudan University, Shanghai, P. R. China
E-mail: gxjin@fudan.edu.cn
Fax: +86-21-65641740
Tel: +86-21-65643776

Abstract

The neutral Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) and zwitterionic Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9) (Cp* = η5-C5Me5, M = Ir, Rh, 1-PPh2-2-S-1,2-C2B10H10 = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH3-7-PPh2-8-S-7,8-C2B9H9 = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane]−) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) (M = Ir (1a), Rh (1b)) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9)] (M = Ir (2a), Rh(2b)). The oxidation of 2b with O2 gas afforded the corresponding sulfone complex 3b in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.

Graphical abstract: Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

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Article information

DOI
https://doi.org/10.1039/B918272A
Article type
Paper
Submitted
03 Sep 2009
Accepted
19 Nov 2009
First published
05 Jan 2010

Dalton Trans., 2010,39, 1954-1961

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Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

X. Huo, G. Su and G. Jin, Dalton Trans., 2010, 39, 1954 DOI: 10.1039/B918272A

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