Synthesis, Structural Properties and Reactivity of Ruthenocene-based Pincer Pd(II) Tetrahydroborate

Safronov, S.V.; Gutsul, E.I.; Golub, I.; Dolgushin, F.M.; Nelyubina, Y.V.; Filippov, O.A.; Epstein, L.M.; Peregudov, A.S.; Belkova, N.; Shubina, E.

Авторы: Safronov Sergey V., Gutsul Evgenii I., Golub Igor, Dolgushin Fedor M., Nelyubina Yulia V., Filippov Oleg A., Epstein Lina M., Peregudov Alexander S., Belkova Natalia, Shubina Elena
Журнал: Dalton Transactions
Том: 48
Номер: 13
Год издания: 2019
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
Первая страница: 12720
Последняя страница: 12729
DOI: 10.1039/c9dt02176k
Аннотация: Two novel ruthenocene-based pincer palladium tetrahydroborates were characterized by XRD, NMR and FTIR. The alcoholysis of Pd(II) tetrahydroborate LPd(BH4) (L= κ3-[{2,5-(tBu2PCH2)2C5H2}Ru(C5H5)]) yields the dinuclear cationic Pd(II) tetrahydroborate with bridging BH4− ligand [(LPd)2(µ,η1,2:η1,2-BH4)]+. The bifurcate dihydrogen-bonded complexes are the active intermediates of the first proton transfer in the step-wise alcoholysis of LPd(BH4) yielding eventually [(LPd)2(µ,η1,2:η1,2-BH4)]+. According to the X-ray DFT/M06 geometry analysis, BH4− ligand in both palladium tetrahydroborates has mixed coordination mode η1,2. The possibility of BH3-group abstraction from LPd(BH4) by an excess of organic base (THF, Py) with the formation of hydride LPdIIH is shown. This Pd (II) hydride is very reactive compound able to rapidly activate CO2 (ca. 15 min) converting into formiate complex LPdII(η1-OC(O)H). Hydrolysis of LPdH with the subsequent CO2 yields hydrocarbonate complex LPdII(η1-OC(O)OH). Hydrocarbonate complex forms hydrogen-bonded dimers in the crystal due to the hydrogen bond between the OC(O)OH fragments.
Добавил в систему: Шубина Елена Соломоновна

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Synthesis, Structural Properties and Reactivity of Ruthenocene-based Pincer Pd(II) Tetrahydroborateстатья

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