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Updated: Dec 23, 2025

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Octaboraneyl Complexes of Nickel: Monomers for Redox-Active Coordination Polymers
Marcus W Drover1, Maeve C Dufour1, Lindsay A Lesperance-Nantau1
1Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor, ON, N9B 3P4, Canada.
Abstract:
Herein, we establish the preparation, characterization, and reactivity of a new diphosphine ligand, 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P2 BCy 4 ), a scaffold that contains four pendant boranes. An entryway into the coordination chemistry of P2 BCy 4 is established by using nickel, providing the octaboraneyl complex [Ni(P2 BCy 4 )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 P2 BCy 4 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.
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