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The international journal for inorganic, organometallic and bioinorganic chemistry
Paper
Dalton Trans., 2005, 3166 - 3172, DOI: 10.1039/b503153m
Preparation of chalcogenolato-bridged dinuclear Tp*Rh–Cp*Ru complexes (Tp*= hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp*=
5-pentamethylcyclopentadienyl) and binding of dioxygen to their Ru sitesShoken Nagao, Hidetake Seino, Masanobu Hidai and Yasushi Mizobe
Reactions of [Tp*Rh(coe)(MeCN)]( 1; Tp*= hydrotris(3,5-dimethylpyrazol-1-yl); coe = cyclooctene) with one equiv of diphenyl dichalcogenides PhEEPh (E = Se, Te) afforded the mononuclear RhIII complexes [Tp*Rh(EPh)2(MeCN)]( 2b: E = Se; 2c: E = Te), as reported previously for the formation of [Tp*Rh(SPh)2(MeCN)]( 2a) from the reaction of 1 and PhSSPh. Complexes 2a–2c were treated with the RuII complex [(Cp*Ru)4(µ3-Cl)4](Cp*=
5-C5Me5) in THF at room temperature, yielding the chalcogenolato-bridged dinuclear complexes [Tp*RhCl(µ-EPh)2RuCp*(MeCN)]( 3). Complex 3a(E = S) in solution was converted slowly into a mixture of 3a and the sterically less encumbered dinuclear complex [Tp*RhCl(SPh)(µ-1-S-6-Ph)RuCp*]( 4a) at room temperature. In 4a, one SPh group binds only to the Rh center as a terminal ligand, while the other SPh group bridges the Rh and Ru atoms by coordinating to the former at the S atom and to the latter with the Ph group in a 
fashion. The Se analogue 3b also underwent a similar transformation under more forcing conditions, e.g. in benzene at reflux, whereas formation of the µ–1-Te-6-Ph complex was not observed for the Te analogue 3c even under these forcing conditions. When complexes 3 was dissolved in THF exposed to air, the MeCN ligand bound to Ru was substituted by dioxygen to give the peroxo complexes [Tp*RhCl(µ-EPh)2RuCp*(2-O2)]( 5a: E = S; 5b: E = Se; 5c: E = Te). X-Ray analyses have been undertaken to determine the detailed structures for 2c, 3a, 3b, 4a, 5a, 5b, and 5c.
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