Copper(I) Complexes of Bis(2-(diphenylphosphino)phenyl) Ether: Synthesis, Reactivity, and Theoretical Calculations

Abstract

The tricoordinated cationic CuI complex [Cu(κ2-P,P‘-DPEphos)(κ1-P-DPEphos)][BF4] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl) ether) containing a dangling phosphorus center was synthesized from the reaction of [Cu(CH3CN)4][BF4] with DPEphos in a 1:2 molar ratio in dichloromethane. When complex 1 is treated with MnO2, elemental sulfur, or selenium, the uncoordinated phosphorus atom undergoes oxidation to form a PE bond resulting in the formation of complexes of the type [Cu(κ2-P,P‘-DPEphos)(κ2-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu−E bond. The zigzag polymeric CuI complex [Cu(κ2-P,P‘-DPEphos)(μ-4,4‘-bpy)]n[BF4]n (5) was prepared by the reaction of [Cu(CH3CN)4][BF4] with DPEphos and 4,4‘-bipyridine in an equimolar ratio. The stereochemical influences of DPEphos on its coordination behavior are examined by density functional theory calculations.