C–Cl activation of the weakly coordinating anion [B(3,5-Cl2C6H3)4]− at a Rh(i) centre in solution and the solid-state

Abstract

Addition of H₂ to [Rh(ⁱBu₂PCH₂CH₂PⁱBu₂)(NBD)][BAr^Cl₄] (NBD = norbornadiene, Ar^Cl = 3,5-Cl₂C₆H₃) in the solid-state results in the rapid formation of zwitterionic [Rh(ⁱBu₂PCH₂CH₂PⁱBu₂){(η⁶-C₆H₃Cl₂)BAr^Cl₃}] by a gas/solid reaction. This undergoes slow C–Cl bond cleavage in the solid-state to ultimately afford the dimeric Rh(III) complex [RhCl(ⁱBu₂PCH₂CH₂PⁱBu₂){C₆H₃Cl(BAr^Cl₃)}]₂. This reactivity is mirrored in solution (CH₂Cl₂). Kinetic data for the C–Cl activation in both the solid-state and solution are reported.