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• W2144195430 endingPage "938" @default.
• W2144195430 startingPage "929" @default.
• W2144195430 abstract "The electrochemical oxidation of [Mo2(cp)2(μ-SMe)3(μ-N2Ph)] and [Mo2(cp)2(μ-SMe)3(μ-N2HPh)]+ complexes where the diazo bridge adopts either an η1 or an η1:η1 coordination mode has been studied by cyclic voltammetry and controlled-potential electrolysis in THF– and CH2Cl2–[NBu4][PF6]. The electrochemical oxidation of [Mo2(cp)2(μ-SMe)3(μ-η1-N2Ph)] 1 and of [Mo2(cp)2(μ-SMe)3(μ-η1-N2HPh)]+1-H+++ triggers the isomerization of the diazo bridge to the η1:η1 mode found in 2+++ and 2-H2+2+2+ respectively. The electrochemical oxidation of [Mo2(cp)2(μ-SMe)3(μ-η1:η1-N2Ph)] 3 and of [Mo2(cp)2(μ-SMe)3(μ-η1:η1-HN2Ph)]+3-H+++ with a syn (“up–up”) arrangement of the Me substituents of the equatorial sulfur bridges is also followed by an isomerization to 2+++ and 2-H2+2+2+, respectively, with an anti (“up–down”) configuration of the equatorial Me groups. The rates of the isomerization 1++ → 2+++, 1-H2+2+2+ → 2-H2+2+2+, and 3-H2+2+ → 2-H2+2+2+ were studied by cyclic voltammetry at different scan rates and at different temperatures. The isomerization of the protonated complexes with either a hydrazido(2−) or a diazene bridge (respectively 1-H2+2+2+ and 3-H2+2+) is faster than that of the diazenido precursors (respectively 1++ and 3++). The diazenido complex 2+++ protonates readily, affording 2-H2+2+2+, while 2-H3+3+ undergoes proton loss." @default.
• W2144195430 created "2016-06-24" @default.
• W2144195430 creator A5052002647 @default.
• W2144195430 creator A5058468705 @default.
• W2144195430 creator A5061799367 @default.
• W2144195430 creator A5068579932 @default.
• W2144195430 creator A5083781756 @default.
• W2144195430 date "2006-01-01" @default.
• W2144195430 modified "2023-10-15" @default.
• W2144195430 title "Oxidatively-induced μ-η¹→ μ-η¹:η¹rearrangement of {NN} ligands at a {Mo₂(μ-SMe)₃} site and protonation of the oxidized diazenido complex" @default.
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