Probing Stepwise Reaction of NNP鈥揕igand Copper(I) Complex with Elemental Sulfur by Using N-Heterocyclic Carbene as a Trapper

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• 作者：Gengwen Tan ; Hongping Zhu
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：August 1, 2011
• 年：2011
• 卷：50
• 期：15
• 页码：6979-6986
• 全文大小：958K
• 年卷期：v.50,no.15(August 1, 2011)
• ISSN：1520-510X

文摘

The dinuclear NNP鈥搇igand copper(I) complex [o-N鈺怌H(C₄H₃N)鈥揚Ph₂C₆H₄]₂Cu₂ (1) has been synthesized by the reaction of (CuMes)₄ (Mes = 2,4,6-Me₃C₆H₂) with N-((1H-pyrrol-2-yl)-methylene)-2-(diphenylphosphino)benzenamine under an elimination of MesH. Further reaction of 1 with an excess of S₈ produced a mononuclear Cu(II) complex [o-N鈺怌H(C₄H₃N)鈥揚(S)Ph₂C₆H₄]₂Cu (5) and CuS. CuS was identified by Raman spectroscopy and 1 and 5 were clearly confirmed by X-ray crystallography. The N-heterocyclic carbene was employed to react with 1 to give a mononuclear [o-N鈺怌H(C₄H₃N)鈥揚Ph₂C₆H₄]Cu{C[N(iPr)CMe]₂} (2). The reactions of 2 were carried out with ¹/₈, ²/₈, and ⁵/₈ equiv of S₈, leading to compounds [o-N鈺怌H(C₄H₃N)鈥揚(S)Ph₂C₆H₄]Cu{C[N(iPr)CMe]₂} (3), [o-N鈺怌H(C₄H₃N)鈥揚(S)Ph₂C₆H₄]Cu (4), and 5 respectively, in which CuS was generated in the third reaction and S鈺怌[N(iPr)CMe]₂ in the latter two reactions. The clean confirmation of 2鈥?b>4 demonstrates a stepwise reaction process of 1 with S₈ to 5 and CuS and the N-heterocyclic carbene acts well as a trapping agent.