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Lyubov DM, Cherkasov AV, Fukin GK, et al. Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization. Dalton Trans. 2014;43(38):14450-60doi: 10.1039/c4dt00806e.
Lyubov, D. M., Cherkasov, A. V., Fukin, G. K., Ketkov, S. Y., Shavyrin, A. S., & Trifonov, A. A. (2014). Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization. Dalton transactions (Cambridge, England : 2003), 43(38), 14450-60. https://doi.org/10.1039/c4dt00806e
Lyubov, Dmitry M, et al. "Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization." Dalton transactions (Cambridge, England : 2003) vol. 43,38 (2014): 14450-60. doi: https://doi.org/10.1039/c4dt00806e
Lyubov DM, Cherkasov AV, Fukin GK, Ketkov SY, Shavyrin AS, Trifonov AA. Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization. Dalton Trans. 2014 Oct 14;43(38):14450-60. doi: 10.1039/c4dt00806e. PMID: 24983231.
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Dalton Trans. 2014 Oct 14;43(38):14450-60. doi: 10.1039/c4dt00806e.

Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization.

Dalton transactions (Cambridge, England : 2003)

Dmitry M Lyubov, Anton V Cherkasov, Georgy K Fukin, Sergey Yu Ketkov, Andrey S Shavyrin, Alexander A Trifonov

Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina str., 603950, Nizhny Novgorod, GSP-445, Russia. [email protected].

PMID: 24983231 DOI: 10.1039/c4dt00806e

Abstract

The reaction of Ap(9Me)Lu(CH2SiMe3)2(thf) (Ap(9Me) = (2,4,6-trimethylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) with two molar equivalents of PhSiH3 affords a trinuclear alkyl-hydrido cluster [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2]. The analogous reactions with Ap(9Me)Ln(CH2SiMe3)2(thf) (Ln = Y, Yb) are more complex and result in the formation of mixtures of two types of trinuclear alkyl-hydrido complexes [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiH2Ph)(thf)2] differing in the alkyl group. The DFT calculations of [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] (Ap* = (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) confirm localization of the HOMO on the Ap*-Y(1A)-CH2SiMe3 fragment, thus explaining its enhanced reactivity. Analysis of the electron density distribution reveals the Y-H and H-H bonding interactions in the (Y)3(μ(2)-H)3(μ(3)-H)2 moiety. The NMR studies of diamagnetic complexes [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] demonstrated that the trinuclear cores are retained in the solution and revealed exchange between μ(3)- and μ(2)-bridging hydrido ligands. Complexes [(Ap*Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2], the cationic yttrium hydrido cluster [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(thf)3](+)[B(C6F5)4](-) as well as [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] proved to be active in catalysis of ethylene polymerization under mild conditions.

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