TETRAETHYLPHYROPHOSPHITE AS A BRIDGING LIGAND IN A BIMETALLIC RUTHENIUM(II) - RUTHENIUM(II) COMPLEX

Abstract

The complex μ-TEPP-trans-bis[P(OEt)₃Ru(NH₃)₄]₂(PF₆)₄ has been prepared and characterized by microanalysis, vibrational and electronic spectroscopy (λ_max=299 nm, ∊=6.4 × 10² M⁻¹ cm⁻¹; λ_max=262 nm, ∊=8.6 × 10² M⁻¹ cm⁻¹), and cyclic voltammetry (E°'=+0.64 V versus S.C.E., 25°, μ=0.10 M NaCf₃COO, C_H+=1 × 10⁻³ M). In aqueous solutions, ([H⁺] > 1 × 10⁻⁴ M), the binuclear species undergoes hydrolysis yielding the mononuclear species trans-(Ru(NH₃)₄P(OEt)₃(H₂O)]²⁺ with a specific rate constant of 2.4 × 10⁻⁵ sec⁻¹ at 25° δH^#=84.5 kJ mol⁻¹; δS^#=−49.4 J mol⁻¹ K⁻¹.