Redox Properties of Binuclear Rhenium-Platinum Vinylidene Complexes with Phosphorus Containing Ligands

Abstract

The redox properties of new binuclear μ-vinylidene complexes Cp(CO)

Electrochemically induced transformations of bi- and trinuclear heterometallic vinylidene complexes containing Re, Pd and Fe

“…The half wave oxidation potential value of the second oxidation stage of 2-4 at the Ptand GC-electrodes coincides with the oxidation potential value (Е 1/2 = 0.33 V) of mononuclear complex 1 [58]. This demonstrates that the one-electron oxidation of the binuclear RePd complexes results in 1 in quantitative yield, which is clearly confirmed by the presence of two…”

“…The results of the electrochemical study of binuclear μ-vinylidene complexes Cp(CO) 2 MnM(-C=CHPh)LL (M = Pt, Pd, L, L = CO, P(OPr-i) 3, PPh 3, P(OPh) 3 , L-L = Ph 2 P(CH 2 ) n PPh 2 , n = 1 (dppm), 2 (dppe), 3 (dppp)) [52][53][54][55][56][57], Cp(CO) 2 RePt(μ-C 1 =C 2 HPh)L 2 (L 2 = 2 PPh 3 , dppm, dppe, dppp) [58], dimeric compounds [Cp(CO) 2 M(µ-C=CHPh)CuCl] 2 (M = Mn, Re) [59][60][61] and trinuclear clusters CpMnFePt( 3 -C=CHPh)(CO) 5 LL ' (L, L ' = CO, PPh 3 , P(OPr-i) 3 , L-L = dppm) [53][54][55][56] were reported in our previous papers. The redox properties of vinylidene clusters ( 3 -C=CHPh)FeCo 2 (CO) 7 dppm, ( 3 -C=CHPh)FeCo 2 (CO) 9 [62,63].…”

Chemistry of vinylidene complexes. XXV. Synthesis and reactions of binuclear µ-vinylidene RePt complexes containing phosphite ligands. Spectroscopic, structural and electrochemical study

“…2b, peak B 2 ) coincides with the oxidation potential value (Е 1/2 = 0.33 V) of the mononuclear rhenium vinylidene complex (Table 5, Fig. 2d, peak D 1 ) [38,39]. This demonstrates that the oneelectron oxidation of the binuclear RePt complexes (1a-3b, 4) results in decomposition of those to Cp(CO) 2 Re=C=CHPh.…”

“…The bis-vinylidene rhenium complex was shown to be generated only under the treatment of Cp(CO) 2 Re=C=CHPh with [(η 5 -C 5 H 5 ) 2 Fe]BF 4 /triethylamine couple in dichloromethane at room temperature [39]. Moreover, the controlled potential electrolysis at a Pt-electrode of µ-vinylidene RePt and RePd complexes with chelate diphosphine ligands resulted in only the formation of Cp(CO) 2 Re=C=CHPh, the second pathway yielding the rhenium cation-radical [Cp(CO) 2 Re=C=CHPh] +• and its dehydrodemirization product Cp(CO) 2 Re=C=C(Ph)-C(Ph)=C=Re(CO) 2 Cp wasn't observed at all [28,38,41]. Therefore, the formation of Cp(CO) 2 Re=C=C(Ph)-C(Ph)=C=Re(CO) 2 Cp under the electrochemical conditions can be explained by specific behavior of the generated cation radicals [Cp(CO) 2 Re=C=CHPh] +• and the platinum fragments on the surface of the platinum electrode.…”