Spectroscopic Characterization of Primary and Secondary Phosphine Ligation on Ruthenium(II) Complexes

Ruthenium(II) complexes of the primary phosphines PH2Fc and PH2CH2Fc and the secondary phosphine PH(CH2Fc)2, including [(p-cymene)RuCl(L)2](PF6) (p-cymene = p-iPrC6H4Me, L = PH2CH2Fc and PH(CH2Fc)2, 2b
and 2c, respectively) and trans-[RuCl2(L)4] (L = PH2Fc, PH2CH2Fc, and PH(CH2Fc)2, 3a−c, respectively) were
prepared and characterized by IR, 1H NMR, and 31P NMR spectroscopy. 3b was additionally characterized by
X-ray crystallography. The spectroscopic effects of phosphine ligation were determined. Characteristic downfield
shifts of the 31P NMR resonances and increases in energy of the ν(P−H) modes were observed in all cases.
Iterative fitting of coupling constants to second-order NMR spectra also resulted in a complete elucidation of 31P−1H and 31P−31P couplings. This analysis provides a basis for considering the influence of coordinate bonding on
the observed 1JPH and 2JPP constants.