The mixed chloro-bromo-rhodates(III) [RhClnBr6-n]3-, n = 1-5, have been separated for the first time by ion exchange chromatography on diethylaminoethyl-cellulose. Due to the stronger trans-effect of Br, as compared with Cl, on treatment of [RhBr6]3- with conc. HCl nearly pure cis/fac-isomers for n = 2, 3, 4 are formed. The reaction of [RhCl6]3- with conc. HBr yields mixtures of the cis/trans-isomers for n = 2, 4, which cannot be separated, but mer-[RhCl3Br3]3 is formed stereospecifically. The IR and Raman spectra of all isolated mixed ligand complexes are completely assigned according to point groups Oh, D3d, C4v, C3v and C2v, supported by normal coordinate analyses based on a general valence force field. The good agreement of calculated and observed frequencies confirms the assignments. Due to the stronger trans-influence of Br as compared to Cl, in all asymmetric Cl—Rh—Br axes the Rh—Br bonds are strengthened and the Rh—Cl bonds are weakened, indicated by valence force constants for Rh—Br approximately 14% higher, for Rh—Cl 10% lower, as compared with the values calculated for symmetric Br—Rh—Br and Cl—Rh—Cl axes, respectively.
Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*MIII(L)XY] (M = Rh, Ir) Complexes with CO, CN–, and CNR Ligands. A Window to Cis Influence
