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Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Str., Moscow 119991, Russia
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Molecules 2020, 25(9), 2236; https://doi.org/10.3390/molecules25092236
Received: 21 April 2020 / Revised: 6 May 2020 / Accepted: 7 May 2020 / Published: 9 May 2020
(This article belongs to the Section Organometallic Chemistry)
Ruthenocene-based PCPtBu pincer ligands were used to synthesize novel pincer palladium chloride RcF[PCPtBu]PdCl (2a) and two novel palladium tetrahydroborates RcF[PCPtBu]Pd(BH4) (3a) and Rc*[PCPtBu]Pd(BH4) (3b), where RcF[PCPtBu] = κ3-{2,5-(tBu2PCH2)2-C5H2}Ru(CpF) (CpF = C5Me4CF3), and Rc*[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp*) (Cp* = C5Me5). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCPtBu]Pd(BH4) analogue (3c; where Rc[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp), Cp = C5H5) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c < 3b < 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH4 ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η1,2. The strength of the BH4 bond with palladium atom increases in the order Rc[PCPtBu]Pd(BH4) < Rc*[PCPtBu]Pd(BH4) < RcF[PCPtBu]Pd(BH4) that appears to be affected by both steric and electronic properties of the ruthenocene moiety. View Full-Text
Keywords: pincer; ligand; palladium; ruthenocene; tetrahydroborate pincer; ligand; palladium; ruthenocene; tetrahydroborate
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MDPI and ACS Style

Safronov, S.V.; Osipova, E.S.; Nelyubina, Y.V.; Filippov, O.A.; Barakovskaya, I.G.; Belkova, N.V.; Shubina, E.S. Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides. Molecules 2020, 25, 2236. https://doi.org/10.3390/molecules25092236

AMA Style

Safronov SV, Osipova ES, Nelyubina YV, Filippov OA, Barakovskaya IG, Belkova NV, Shubina ES. Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides. Molecules. 2020; 25(9):2236. https://doi.org/10.3390/molecules25092236

Chicago/Turabian Style

Safronov, Sergey V., Elena S. Osipova, Yulia V. Nelyubina, Oleg A. Filippov, Irina G. Barakovskaya, Natalia V. Belkova, and Elena S. Shubina 2020. "Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides" Molecules 25, no. 9: 2236. https://doi.org/10.3390/molecules25092236

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