In situ FTIRS studies of reduction of [OsVI(N)(NH3)4](CF3SO3)3 in acetonitrile

Abstract

运用原位FTIRS ,UV/Vis和电化学方法研究了乙腈溶液中 [OsⅥ(N) (NH3 ) 4](CF3 SO3 ) 3 在GC和Pt电极上的还原过程。结果首次在Pt电极上检测到桥氮物种ν(N≡N)的红外谱峰 ,位于 2 0 19和 1970cm-1附近 ,分别指认为 [Ⅲ ,Ⅱ ]和 [Ⅱ ,Ⅱ ]混合价桥氮锇络合物。为进一步探讨桥氮偶联过程提供了新的谱学数据 In this paper,the electrochemical cyclic volta mm etry,UV/Vis and in situ FTIR spectroscopy were used to study the electrochemical reduction of [Os-Ⅵ(N)(NH 3) 4](CF 3SO 3) 3 on GC and Pt electro de in acetonitrile.The results demonstrated that the N-N coupling can occur bet ween [Os-Ⅵ(N)(NH 3) 4]- 3+ and the osmium(V) species generated at the electrode.It has revealed for the first time,by in situ FTIR spectroscopy,t hat the IR absorption of the ν(N≡N) mode of the μ-dinitrogen osmium[Ⅲ ,Ⅱ]and [Ⅱ,Ⅱ] complex yields positive-going band at around 2 019 cm- -1 and negative-going band near 1 970 cm- -1,respectively.The results provided new insights in understanding the mechanism of the coupling reaction [Os-Ⅴ≡N][Os-Ⅵ≡N][Os-Ⅱ-N≡N-Os-Ⅲ].