Gas-Phase Reactivity of Coordinatively Unsaturated Transition Metal Complex Ions toward Molecular Oxygen
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- 作者：Henrik Molina-Svendsen ; Gustav Bojesen ; and Christine J. McKenzie
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：April 20, 1998
- 年：1998
- 卷：37
- 期：8
- 页码：1981 - 1983
- 全文大小：42K
- 年卷期：v.37,no.8(April 20, 1998)
- ISSN：1520-510X
文摘
Electrospray mass spectrometry is used to investigate thereactivity of the coordinatively unsaturated ions[M(bipy)2]2+ (M = Cr, Ru, Os) and[M(bipy)]+ (M = Co, Ni) toward O2 to givethe dioxygen adducts[M(bipy)2O2]2+ (M = Cr, Ru,Os) and [M(bipy)O2]+ (M = Co, Ni).CID experiments with the[M(bipy)2O2]2+and [M(bipy)O2]+ adducts show that theloss of a mass equivalent to two oxygen atoms is thepredominantprocess for [M(bipy)2O2]2+ (M= Cr, Ru) and [M(bipy)O2]+ (M =Ni, Co). In contrast, weak signals assignedto [Os(bipy)O2]+,[Os(bipy)O2]2+, andbipy+
indicate loss of a bipyridine ligandfrom [Os(bipy)2O2]2+ratherthan O2 loss. This result may have structuralimplications and a dioxo Os(VI) complex cation,[Os(bipy)2(O)2]2+,is proposed for the Os-dioxygen adduct. This assignment isconsistent with the known solution and solid-statechemistry of osmium. Formation of[OsVI(bipy)2(O)2]2+involves a formal oxidation of the Os(II) to anOs(VI)and concomitant O2 four-electron reduction ofO2. Even though loss of O2 rather thanbipy was the predominantprocess observed in CID experiments for the Ru adduct, a structuralformulation of an analogous dioxo speciesis not excluded for[Ru(bipy)2O2]2+.
indicate loss of a bipyridine ligandfrom [Os(bipy)2O2]2+ratherthan O2 loss. This result may have structuralimplications and a dioxo Os(VI) complex cation,[Os(bipy)2(O)2]2+,is proposed for the Os-dioxygen adduct. This assignment isconsistent with the known solution and solid-statechemistry of osmium. Formation of[OsVI(bipy)2(O)2]2+involves a formal oxidation of the Os(II) to anOs(VI)and concomitant O2 four-electron reduction ofO2. Even though loss of O2 rather thanbipy was the predominantprocess observed in CID experiments for the Ru adduct, a structuralformulation of an analogous dioxo speciesis not excluded for[Ru(bipy)2O2]2+.