C. Diaz et A. Arancibia, MONODENTATE AND BRIDGING BEHAVIOR OF DINITRILES LIGANDS TOWARD THE FRAGMENT CP(DPPE)FE+, Boletin de la Sociedad Chilena de Quimica, 43(3), 1998, pp. 303-314
The reaction of Cp(dppe)Fel with the dinitriles NC(CH2)(n)CN n = 3, 4,
6 in CH3OH and using NH4PF6 as halide abstractor afford the monodenta
te dinitrile complexes [Cp(dppe)Fe- (eta(1)-NC(CH2)(n)CN)PF6. Treatmen
t of these mononuclear complexes with Cp(dppe)Fel afford the binuclear
complexes [Cp(dppe)Fe-NC(CH2)(n)CN-Fe(dppe)Cp](PF6)(2). All the new p
roducts were characterized by elemental analysis as well as IR, H-1- P
-31- and C-13-NMR spectroscopy and by UV-visible as well as cyclic vol
tammetry studies. The coordinative properties of nitriles were conveni
ently discussed using the C-13-NMR data and MO arguments, finding that
the ligands behave mainly as sigma-donor. In the binuclear complexes
the two Cp(dppe)Fe+ fragments are identical observing in the cyclic vo
ltammogram only one oxidation wave. The high symmetry of the binuclear
complexes is also corroborated by the spectroscopic results. Electroc
hemical results suggest no interaction between the metal centers.