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Ln(ii) and Ca(ii) NCsp3N pincer type diarylmethanido complexes – promising catalysts for C–C and C–E (E = Si, P, N, S) bond formation

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Abstract

Ln(II) (Ln = Yb, Sm) and Ca(II) [NCsp3N] pincer type diarylmethanido complexes [2,2′-(4-MeC6H3NMe2)2CH]2M (M = Yb (2), Sm (3), Ca (4)) coordinated by a tridentate diarylmethanido ligand were synthesized through salt metathesis reactions of {[2,2′-(4-MeC6H3NMe2)2CH]K(THF)}2 and MI2(THF)2. X-ray analysis revealed that both diarylmethanido ligands in 2–4 are tridentate and coordinate to the metal centers via central carbon and two nitrogen atoms of NMe2 groups resulting in [NCsp3N] pincer coordination. In one of the five-membered MCCCN metallacycles in each tridentate diarylmethanido ligand, metal–arene interactions were detected and the coordination mode of [NCsp3N] ligands in 2–4 can be classified as κ1-N:η4-CCCN. A dynamic behavior involving the exchange between NMe2 groups and THF molecules in the coordination sphere of the M(II) ion was detected in solution. Complexes 2–4 proved to be catalytically active in a variety of reactions of C–C and C–E (E = Si, P, N, S) bond formation. Yb(II) 2 and Ca(II) 4 complexes catalyze intermolecular hydrobenzylation of styrene with 2-methyl and 2,6-dimethyl pyridines. Complex 2 demonstrates high chemo- and regioselectivities and is the first Ln(II) catalyst for intermolecular C–C bond formation. Complexes 2–4 were found to be efficient and selective precatalysts for intermolecular hydroelementation of olefins and acetylenes with various EH substrates (E = Si, P, N, S). Complexes 2–4 have demonstrated their versatility for intermolecular C–E bond formation and allow the realization of hydroamination, hydrophosphination, hydrosilylation and hydrothiolation of styrene and phenylacetylene. Moreover, 2–4 were found to be active in the catalysis of challenging transformations such as hydrosilylation and hydrophosphination of internal double C[double bond, length as m-dash]C and triple C[triple bond, length as m-dash]C bonds.

Graphical abstract: Ln(ii) and Ca(ii) NCsp3N pincer type diarylmethanido complexes – promising catalysts for C–C and C–E (E = Si, P, N, S) bond formation

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Article information


Submitted
30 Mar 2020
Accepted
11 May 2020
First published
12 May 2020

Inorg. Chem. Front., 2020, Advance Article
Article type
Research Article

Ln(II) and Ca(II) NCsp3N pincer type diarylmethanido complexes – promising catalysts for C–C and C–E (E = Si, P, N, S) bond formation

D. O. Khristolyubov, D. M. Lyubov, A. S. Shavyrin, A. V. Cherkasov, G. K. Fukin and A. A. Trifonov, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QI00369G

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