Zusammenfassung
Vaska-type complexes, i.e. trans-[RhX(CO)(PPh3)(2)] (X is a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the Rh I atom 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 ...
Zusammenfassung
Vaska-type complexes, i.e. trans-[RhX(CO)(PPh3)(2)] (X is a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the Rh I atom 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-kappa N)bis(triphenylphosphine-kappa P)rhodium(I), [Rh(NCBH3)(CO)-(C18H15P)(2)], was prepared by the metathesis reaction of sodium cyanotrihydridoborate with trans-[RhCl(CO)(PPh3)(2)], and was characterized by singlecrystal X-ray diffraction analysis and IR, H-1, C-13 and B-11 NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the Rh I atom through the N atom in a trans position with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency v(CO) and the carbonyl carbon (1)J(C-Rh) and (1)J(C-P) coupling constants of the C-ipso atoms of the triphenylphosphine groups reflect the diminished electron density on the central Rh I atom compared to the parent trans-[RhCl(CO)(PPh3)(2)] complex.
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