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Issue 33, 2019
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Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(II) tetrahydroborate

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Abstract

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 the bridging BH4 ligand [(LPd)2(μ,η1,21,2-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,η1,21,2-BH4)]+. According to the X-ray and DFT/M06 geometry analysis, the BH4 ligand in both palladium tetrahydroborates has a 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 a very reactive compound able to rapidly capture CO2 (ca. 15 min) converting into the formate complex LPdII1-OC(O)H). The hydrolysis of LPdH with subsequent CO2 insertion yields a hydrocarbonate complex LPdII1-OC(O)OH). The hydrocarbonate complex forms hydrogen-bonded dimers in the crystal due to hydrogen bonds between the OC(O)OH fragments.

Graphical abstract: Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(ii) tetrahydroborate

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Publication details

The article was received on 23 May 2019, accepted on 29 Jul 2019 and first published on 29 Jul 2019


Article type: Paper
DOI: 10.1039/C9DT02176K
Dalton Trans., 2019,48, 12720-12729

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    Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(II) tetrahydroborate

    S. V. Safronov, E. I. Gutsul, I. E. Golub, F. M. Dolgushin, Y. V. Nelubina, O. A. Filippov, L. M. Epstein, A. S. Peregudov, N. V. Belkova and E. S. Shubina, Dalton Trans., 2019, 48, 12720
    DOI: 10.1039/C9DT02176K

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