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

The tricoordinated cationic Cu-I complex [Cu(kappa(2)-P,P'-DPEphos)(kappa(1)-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(kappa(2)-P,P'-DPEphos)(kappa(2)-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu-E bond. The zigzag polymeric Cu-I complex [Cu(kappa(2)-P,P'-DPEphos)(mu-4,4'-bpy)](n)[BF4](n) (5) was …