Ortho‐F,F‐DPEphos: Synthesis and Coordination Chemistry in Rhodium and Gold Complexes, and Comparison with DPEphos

Abstract

The synthesis of a new ortho‐fluorine substituted diphosphine ligand based upon the DPEphos ligand is reported: o‐F,F‐DPEphos (DPEphos=bis(2‐diphenylphosphinophenyl)ether). The corresponding bimetallic gold complex Au2Cl2(o‐F,F‐DPEphos) and Schrock‐Osborn type Rh(I) complex [Rh(o‐F,F‐DPEphos)(NBD)][BArF4] have been synthesized (ArF=3,5‐(CF3)2‐C6H3). The solid‐state and solution phase NMR data are examined in comparison with the o‐H,H‐DPEphos equivalents, and demonstrate the influence of ortho‐fluorine substitution through the control of aurophilic and Rh⋅⋅⋅X interactions (X=H or F). Characterization of the organometallic products upon hydrogenation of the Schrock‐Osborn complexes in 1,2‐F2C6H4 revealed a Rh dimeric complex [Rh(H)(fac‐κ3‐P,O,P‐μ‐CH‐DPEphos)]2[BArF4]2 with a bridging C−H agostic interaction for the parent DPEphos. The substituted variant formed a Rh(III) monomer [Rh(mer‐κ3‐P,O,P‐o‐F,F‐DPEphos)H2][BArF4], highlighting the structural consequences of ortho‐fluorine substitution.