Characterization and nonrigid behaviour of a carboxylate-bridged rhodium dimer

Abstract

Bis(μ-t-butylacetato)bis(norbornadiene)dirhodium(I) 1 is prepared by a reaction between pivaloyl camphor and (norbornadiene)rhodium(I) chloride dimer. A molecular rearrangement takes place in which the pivaloyl groups of the pivaloyl camphor starting material are incorporated into the end product as bridging t-butylcarboxylate ligands. A variable temperature 1H NMR study and corresponding dynamic computer fit of the NMR data, and crystal structure are reported for the structurally nonrigid dimer. Crystals of 1 are triclinic, a = 10.454(1), b = 10.817(1), c = 12.424(1) Å, α = 64.904(7), β = 100.320(7), γ = 109.382(8)°, Z = 2, space group [Formula: see text] The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.070 and Rw = 0.081 for 3093 reflections with I ≥ 3σ(I).