SITE-SPECIFIC ION-PAIRING OF MONOSUBSTITUTED VANADIUM CARBONYLATES, LV(CO)5-
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Analysis of v(CO) infrared spectra has shown that Na+ cation interacts specifically with the CO group trans to substituent ligands of LV(CO)5 (L = PPh3, P(OPh)3) P(n-Bu)3 and CNMe). Such site selectivity was predicted on the basis of asymmetric electron distribution in such anions as reflected in calculated Cotton-Kraihanzel CO stretching force constants. The Et4N+ cation was also found to form a close interaction with LV(CO)5; however, the specific geometrical form could not be discerned. P-donor ligand substitution reactions of PV(CO)5 were found to follow a dissociative mechanism. Vanadium-phosphorus bond cleavage was counterion dependent, with the tightly interacting Na+ promoting faster dissociation rates. 1982, American Chemical Society. All rights reserved.