TY - JOUR

T1 - Chemistry of vinylidene complexes. XXV. Synthesis and reactions of binuclear mu-vinylidene RePt complexes containing phosphite ligands. Spectroscopic, structural and electrochemical study

AU - Chudin, Oleg S.

AU - Verpekin, Victor V.

AU - Kondrasenko, Alexander A.

AU - Burmakina, Galina

AU - Piryazev, Dmitry A.

AU - Vasiliev, Alexander D.

AU - Pavlenko, Nina

AU - Zimonin, Dmitry

AU - Rubaylo, Anatoly

PY - 2020/5/24

Y1 - 2020/5/24

N2 - Reactions of Cp(CO)(2)Re=C=CHPh with Pt[P(OR)(3)](4) (R = Pr-i, Et, Ph) gave binuclear mu-vinylidene complexes Cp(CO)(2)RePt(mu-C=CHPWW(OR)(3)](2). Treatment of the previously synthesized Cp(CO)(2)Re(mu-C=CHPh)Pt(PPh3)(2) with triisopropylphosphite or triethylphosphite resulted in a stepwise substitution of PPh3 ligands, leading to the disubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)](2) and monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)] (PPh3) (R = Pr-i or Et) species, while no triphenylphosphine ligand substitution in the reaction with P(OPh)(3) occurs at all. The monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](PPh3) (R = Pe(i), Et, Ph) species were also obtained by reacting Cp(CO)(2)Re=C=CHPh with mixed-ligand complexes Pt(PPh3)(3)L (L = P(OPi)(3), P(OEt)(3), P (OPh)(3)). Reactions of Cp(CO)(2)RePt(mu-C=CHPh)LL' = L' = P(OPri)(3), P(OEt)(3), P(OPh)(3); L = P(OPri)(3), P(OEt)(3), P(OPh)(3), L' = PPh3) with Co-2(CO)(9) yield tricarbonyl vinylidene species Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](CO) (R = Pr-i, Et, Ph). The obtained compounds were characterized by IR and H-1, C-13, P-31 NMR spectroscopy. The molecular structures of Cp(CO)(2)RePt(mu-C=CHPh)[P(OPi)(3)](2), Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](PPh3) and Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](CO) were determined by X-ray diffraction study. The redox properties of the new complexes and their reactions of chemical oxidation were studied.

AB - Reactions of Cp(CO)(2)Re=C=CHPh with Pt[P(OR)(3)](4) (R = Pr-i, Et, Ph) gave binuclear mu-vinylidene complexes Cp(CO)(2)RePt(mu-C=CHPWW(OR)(3)](2). Treatment of the previously synthesized Cp(CO)(2)Re(mu-C=CHPh)Pt(PPh3)(2) with triisopropylphosphite or triethylphosphite resulted in a stepwise substitution of PPh3 ligands, leading to the disubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)](2) and monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)] (PPh3) (R = Pr-i or Et) species, while no triphenylphosphine ligand substitution in the reaction with P(OPh)(3) occurs at all. The monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](PPh3) (R = Pe(i), Et, Ph) species were also obtained by reacting Cp(CO)(2)Re=C=CHPh with mixed-ligand complexes Pt(PPh3)(3)L (L = P(OPi)(3), P(OEt)(3), P (OPh)(3)). Reactions of Cp(CO)(2)RePt(mu-C=CHPh)LL' = L' = P(OPri)(3), P(OEt)(3), P(OPh)(3); L = P(OPri)(3), P(OEt)(3), P(OPh)(3), L' = PPh3) with Co-2(CO)(9) yield tricarbonyl vinylidene species Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](CO) (R = Pr-i, Et, Ph). The obtained compounds were characterized by IR and H-1, C-13, P-31 NMR spectroscopy. The molecular structures of Cp(CO)(2)RePt(mu-C=CHPh)[P(OPi)(3)](2), Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](PPh3) and Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](CO) were determined by X-ray diffraction study. The redox properties of the new complexes and their reactions of chemical oxidation were studied.

KW - Vinylidene complexes

KW - Rhenium

KW - Platinum

KW - NMR

KW - X-ray diffraction

KW - Redox properties

KW - PLATINUM HYDRIDE COMPLEXES

KW - OXIDATIVE DEHYDRODIMERIZATION

KW - HETEROMETALLIC COMPLEXES

KW - UNSATURATED MOLECULES

KW - MANGANESE-PLATINUM

KW - CRYSTAL-STRUCTURES

KW - BRIDGED COMPLEXES

KW - BOND ACTIVATION

KW - METAL COMPLEXES

KW - REACTIVITY

U2 - 10.1016/j.ica.2020.110463

DO - 10.1016/j.ica.2020.110463

M3 - Article

VL - 505

SP - 119463

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -