A quantum chemical study of the effect of phosphine ligand on the structure of the Mn and Fe vinylidene binuclear complex

Abstract

Structures and relative energies of binuclear iron-manganese complexes with the phosphine ligand L, which exist in vinylidene Cp(CO)(L)MnFe(μ-C=CHPh)(CO)4 (2) and benzylidene ketene η4-{C[Mn(CO)(L)Cp]∙ ∙(CO)CHPh}Fe(CO)3 (3) forms are calculated by the B3LYP density functional method. Four isomers with different positions of ligand L relative to the phenyl ring (conformers a and b) and the substituent Ph relative to the С=С bond (conformers E and Z) are considered for each form and their relative stability is determined. It is shown that all isomers of 2 have approximately the same energy (within 4 kcal/mol) whereas the energies of isomers of 3 differ within 21 kcal/mol. Isomer 3Ea in which the PPh3 ligand contacts with the phenyl substituent of the vinylidene group is most energetically favorable. It is found that with an increase in the L ligand size in the order PH3 < PH2Ph < PHPh2 < PPh3 the Mn–P bond length increases to 2.37 A in the most stable isomer of form 3 and to 2.43 A in the isomers of 2 and three conformers of 3. A more substantial increase in the Mn–P bond length in complexes 2 and 3 correlates with their lower stability as compared to isomer Ea of 3, which is consistent with experimental data on the presence of only one conformer 3Ea in solution.