532933-50-9Relevant academic research and scientific papers
Bismuth-halide oxidative addition and bismuth-carbon reductive elimination in platinum complexes containing chelating diphosphine ligands
Nabavizadeh, S. Masoud,Niroomand Hosseini, Fatemeh,Nejabat, Negar,Parsa, Zahra
, p. 13480 - 13489 (2013)
Reaction of BiX3 (X = Cl, Br, I) with [PtMe2(P-P)], (1a, P-P = dppm; 1b, P-P = dppe), occurs easily to yield a mixture of platinum(II) complexes [PtMeX(P-P)], 2, and [PtX2(P-P)], 3, and the binuclear complex [Pt2Me2(μ-X)(μ-dppm) 2]X, 4. On the basis of 31P NMR and UV-vis spectroscopy, a mechanism is proposed in which the rate determining step is conversion of the yellowish Pt(II)-BiX3 adduct BiI3·[PtMe 2(dppm)], A, into the Pt(IV)-Bi(III) intermediate [PtMe 2(BiX2)X(P-P)], IM1. Density functional theory (DFT) studies suggest that intermediate IM1 may be formed in acetone solution which undergoes the Bi-C reductive elimination process before formation of complexes 2 and 3. The structures of intermediates IM1 were theoretically determined using DFT calculations. In dilute acetone solution, as monitored by UV-vis spectroscopy, the oxidative addition processes follow first order kinetics. The overall reaction is slower for heavier halide.
