首页 | 本学科首页   官方微博 | 高级检索  
     


Octaboraneyl Complexes of Nickel: Monomers for Redox-Active Coordination Polymers
Authors:Prof. Marcus W. Drover  Maeve C. Dufour  Lindsay A. Lesperance-Nantau  Rayni P. Noriega  Dr. Kirill Levin  Prof. Robert W. Schurko
Affiliation:1. Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor, ON, N9B 3P4 Canada;2. Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor, ON, N9B 3P4 Canada

Department of Chemistry and Biochemistry, The Florida State University, 102 Varsity Way, Tallahassee, FL, 32306-4390 USA

Abstract:Herein, we establish the preparation, characterization, and reactivity of a new diphosphine ligand, 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P2BCy4), a scaffold that contains four pendant boranes. An entryway into the coordination chemistry of P2BCy4 is established by using nickel, providing the octaboraneyl complex [Ni(P2BCy4)2]—this species contains a boron-rich secondary coordination sphere that reacts readily with Lewis bases. In the case of 4,4′-bipyridine, an air-sensitive coordination polymer is obtained. Characterization of this material by solid-state NMR and EPR spectroscopy reveals the presence of a charge-transfer polymer, which forms as a function of intramolecular Ni→4,4′-bpy electron transfer (ET), providing an array of oxidized nickel sites and reduced 4,4′-bpy radical anion sites. Notably, the related intermolecular reaction between the model fragments [Ni(dnppe)2] (dnppe=1,2-bis(di-n-propylphosphino)ethane) and a bis(boraneyl)-protected 4,4′-bpy, provides no ET. Overall, the P2BCy4 fragment provides a unique opportunity for Lewis base activation, in one case allowing for the facile construction of monomers for incorporation into redox-active macromolecules.
Keywords:ambiphiles  borane  diphosphine ligands  electron transfer  Lewis acids  Lewis bases
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号