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

Abstract

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 nu(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 1J(PH) and 2J(PP) constants.

Hydrophosphination reactions with transition metal ferrocenylphosphine complexes

“…4 We have previously extended this chemistry to the sterically demanding air-stable secondary and tertiary ferrocenylphosphines PH(CH 2 Fc) 2 and P(CH 2 Fc) 3 14 and transition metal complexes thereof. 14,[15][16][17][18][19] FcPH 2 is a remarkably convenient starting material considering its easy synthesis and stability compared with related compounds, but has mostly been neglected. In contrast, the highly reactive PhPH 2 has been used extensively.…”

“…20 We have previously reported the synthesis of [MI 2 (CO) 3 (PH 2 Fc) 2 ] (M = Mo, W), 19 [Cp*TaCl 4 (PH 2 Fc)] 15 (Cp* = C 5 Me 5 ) and [RuCl 2 ( pcymene)(PH 2 Fc)]. 17 Presented below is the synthesis and characterisation of the ferrocenylphosphine transition metal carbonyl complexes [M(CO) 5…”

Syntheses and structures of the tetra-phosphine complexes trans-MCl2(PH3)4 (M = Ru, Os)

“…The distances for the Ru-Cl (2.4275(9) A ˚) and Ru-P (2.3088(7) A ˚) bonds are comparable to those found in the literature. 7,8 The Ru, P and Cl atoms were located and refined anisotropically. The hydrogen atoms of the PH 3 groups were disordered due to rotation of the phosphine ligand about the Ru-P axis.…”

New ferrocenylmethylphosphines – Preparation, characterisation and coordination chemistry of PH(CH2Fc)2, P(CH2Fc)3 [Fc=Fe(η5-C5H5)(η5-C5H4)] and their derivatives

“…We have already shown that the phosphines PH 2 Fc, PH 2 CH 2 Fc, and PH(CH 2 Fc) 2 (=L) react with transition metal complexes with reactive M-X bonds (X = halide) without loss of HX but with clean formation of the corresponding phosphine complexes, such as [Cp R TaCl 4 (L)] (Cp R = C 5 H 4 Me, C 5 Me 5 ) [12], [(p-cymene)RuCl 2 (L)] [3,13], [(p-cymene)Ru(Cl)(L) 2 ](PF 6 ) [14], trans-[Ru(Cl) 2 (L) 4 ] [14], [MI 2 (CO) 3 (L) 2 ] and [MI 2 (CO) 2 (L) 3 ] (M = Mo, W) [15][16][17]. The unexpected formation of the unique complex salt [WI(CO) 2 (PH 2 CH 2 Fc) 4 ]I is another example of the unusual coordinating properties of these phosphines [18].…”