A crystallographic and DFT study on Vaska-type trans-[Rh(CO)Cl(PR3)2] complexes containing flexible ligands: The molecular structure of trans-[Rh(CO)Cl{P(OC6H5)3}2]

An investigation into the effect of the flexibility of substituents on the disorder of the Cl–Rh–CO moiety in Vaska-type trans-[Rh(CO)Cl(PR3)2] complexes is presented. The influence of the packing of the complexes with PR3 = P(CH2C6H5)3, P(OC6H5)3, P(O-2-MeC6H4)3 and P(O-2,6-Me2C6H3)3 was evaluated by comparing the X-ray structures with the results of DFT calculations on these complexes. Reasonable agreement between the calculated and molecular structures was found. A good agreement, however, was found between the calculated and crystallographic structures when comparing the coordination polyhedron around the Rh atom. The main difference between the calculated and solid state structures appeared to be in the orientation of the phenyl groups of the P-donor ligands.