THE COORDINATIVE PROPERTIES OF THE LIGANDS Ph2ECH2EPh2 (E = P, As, Sb) IN CARBONYLVANADIUM COMPLEXES, AND THE MOLECULAR STRUCTURE OF η5-C5H5V(CO)3As2Ph4

Article abstract of DOI:10.1016/S0022-328X(00)83103-4

Photo-reaction between the ligands Ph2ECH2EPh2 (E=P: dppm, E=As: dpam, E=Sb: dpsm), L, and the vanadium complexes η⁵-C5H5V(CO)4 and yields monosubstituted mononuclear (dpsm) and dinuclear, ligand-bridged complexes (dpam, dpsm).With dppm, the final products are disubstituted chelate complexes, but monosubstituted mono- and dinuclear species are formed as intermediates.The shielding of the 51V nucleus decreases in the series dpsm > dppm > dpam and > L > 2μ-L > dppm (=^-, η⁵-C5H5V(CO)4).The half-widths of the NMR signals are greater for dinuclear than for mononuclear complexes.The crystal and molecular structures of η⁵-C5H5V(CO)3As2Ph4 have been determined.The compound crystallizes in the space group P2₁/c with a=1347.8, b=1020.0, c=2085.2 pm and β=82.3 deg.Due to steric crowding, the 51V shielding is low compared to that of <η⁵-C5H5V(CO)3>2μ-dpam.