Front Cover: Ortho‐F,F‐DPEphos: Synthesis and Coordination Chemistry in Rhodium and Gold Complexes, and Comparison with DPEphos (Eur. J. Inorg. Chem. 24/2022)

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 Au 2 Cl 2 (o-F,F-DPEphos) and Schrock-Osborn type Rh(I) complex [Rh(o-F,F-DPEphos)(NBD)][BAr F 4 ] have been synthesized (Ar F = 3,5-(CF 3 ) 2 -C 6 H 3 ). 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-F 2 C 6 H 4 revealed a Rh dimeric complex [Rh(H)(fac-k 3 -P,O,P-μ-CH-DPEphos)] 2 [BAr F 4 ] 2 with a bridging CÀH agostic interaction for the parent DPEphos. The substituted variant formed a Rh(III) monomer [Rh(mer-k 3 -P,O,P-o-F,F-DPEphos)H 2 ][BAr F 4 ], highlighting the structural consequences of ortho-fluorine substitution.