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

Abstract

Ln(II) (Ln = Yb, Sm) and Ca(II) [NCsp3N] pincer type dihenylmethanido complexes [2,2’-(4-MeC6H3NMe2)2CH]2M (M = Yb (2), Sm (3), Ca (4)) coordinated by tridentate diphenylmethanido ligand were synthesized through the salt metathesis reactions of {[2,2’-(4-MeC6H3NMe2)2CH]K(THF)}2 and MI2(THF)2. X-ray analysis revealed that both diphenylmethanido 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. Within one of five-membered MCCCN metallacycles in each tridentate diphenylmethanido ligands 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 consisting in the exchange between NMe2 groups and THF molecules in the coordination sphere of 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 itntermolecular 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 to realize hidroamination, hydrophosphination, hydrosilylation and hydrothiolation of styrene and phenylacetylene. Moreover 2–4 were found to be active in catalysis of challenging transformations such as hydrosilylation and hydrophosphination of internal double C=C and triple C≡C bonds.

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Supplementary files

Article information


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

Inorg. Chem. Front., 2020, Accepted Manuscript
Article type
Research Article

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

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

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