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通过卤素和卤素类似物从 Ni(II) 获得 Pincer 双(碳烯)Ni(IV) 配合物。

Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates.

机构信息

School of Chemical Sciences, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.

出版信息

J Am Chem Soc. 2016 Apr 6;138(13):4290-3. doi: 10.1021/jacs.5b12827. Epub 2016 Mar 25.

Abstract

This communication describes the two-electron oxidation of ((DIPP)CCC)NiX ((DIPP)CCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form ((DIPP)CCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The Ni(IV) complexes have been characterized by a suite of spectroscopic techniques and can readily reduce to the Ni(II) counterpart, allowing for cycling between the Ni(II)/Ni(IV) oxidation states.

摘要

本通讯描述了 ((DIPP)CCC)NiX ((DIPP)CCC = 双(二异丙基苯基-苯并咪唑-2-亚基)苯基;X = Cl 或 Br) 与卤素和卤素替代物的两电子氧化,形成 ((DIPP)CCC)NiX3。这些配合物代表了镍的罕见氧化态,以及通过 Br2 和卤素替代物(苄基三甲基氯化铵三溴化物)来获得这些物质的前所未有的反应途径。Ni(IV)配合物已通过一系列光谱技术进行了表征,并且可以很容易地还原为 Ni(II)对应物,从而允许在 Ni(II)/Ni(IV)氧化态之间循环。

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