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Ruthenium(II) tetraammines, a useful model to compare trans-effect and trans-influence of phosphanes

1988; Elsevier BV; Volume: 145; Issue: 1 Linguagem: Inglês

10.1016/s0020-1693(00)82016-2

1873-3255

José Cardoso do Nascimento Filho, José Milton de Rezende, Benedito dos Santos Lima Neto, Douglas Wagner Franco,

Lanthanide and Transition Metal Complexes

The substitution reaction trans-[Ru(NH3)4P(III)pz]2+ + H2O where P(III) = PEt3, PBu3, PPh3, P(OBu)3 and P(OPh)3 has been studied at 25.0°C, μ = 0.10 NaCF3COO, CH+ = 1.0×10−3 M. Assuming the second order specific rate k1 for the substitution of the water molecule on the coordination sphere for pz as indicative of a relative order of the trans-effect of P(III), the following increasing trans-effect order can be written: P(OPh)3<PPh3<P(OEt)3< P(OBu)3<PBu3<PEt3. The weakening of the Ru(II)pz bond expressed as 1/Keq permits us to write the following order of increasing trans-influence: PEt3<PBu3<P(OBu)3<P(OEt)3∼ PPh3<P(OPh)3. The complex trans-[Ru(NH3)4- (PEt3)(P(OEt)3)](PF6)2 has been isolated and characterized by microanalysis, electronic and voltammetric spectra. The aquation of this complex provides additional support to the generalizations about the influence of π bonding on the trans-influence of phosphanes.