Diminished electron density in the Vaska-type rhodium(I) complextrans-[Rh(NCBH3)(CO)(PPh3)2]

Abstract

Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the RhIatom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN−) complexes of Group 6–8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato-κN)bis(triphenylphosphine-κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate withtrans-[RhCl(CO)(PPh3)2], and was characterized by single-crystal X-ray diffraction analysis and IR,1H,13C and11B NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the RhIatom through the N atom in atransposition with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(CO) and the carbonyl carbon1JC–Rhand1JC–Pcoupling constants of the Cipsoatoms of the triphenylphosphine groups reflect the diminished electron density on the central RhIatom compared to the parenttrans-[RhCl(CO)(PPh3)2] complex.