Calcium complexes with a bulky tris-(2-N-piperidinomethyl)-phenyl)methoxide ligand. Synthesis and catalytic activity in the dearomatization of N-heterocycles

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Abstract

The reaction of equimolar amounts of tris-((2-N-piperidinomethyl)-phenyl)methanol ((2-C5H10NCH2-o-C6H4)3COH) with [(Me3Si)2N]2Ca(THF)2 (toluene, 23○C) allows to obtain a mixed-ligand calcium alkoxide-amide complex [(2-C5H10NCH2C6H4)3CO]CaN(SiMe3)2 (I) in 70% yield. X-ray diffraction analysis showed that in I the monoanionic alkoxide ligand is coordinated to the metal in the κ3-O,N,N-fashion. Complex I catalyzes the addition of PhSiH3 to annelated N-containing heterocycles: quinoline, 4-methylquinoline, 6-methylquinoline and isoquinoline. The reactions are chemo- and regioselective and are completd within 24-120 hours. The reaction of I with PhSiH3 (molar ratio 1 : 2) leads to the formation of the bis(alkoxide) complex [κ2-O,N-(2-C5H10NCH2C6H4)3CO]2Ca (II) and CaH2, which are the result of symmetrization of the intermediately formed calcium alkoxyhydride complex. In the crystal, complex II has a nonlinear structure with an OCa(1)O angle of 112.65(4)○, and only one of the piperidine fragments of both ligands is coordinated to the metal ion. The molecular structure of complexes I and II was established using X-ray diffraction (CCDC № 2443979 (I), 2443980 (II)).

About the authors

A. N. Selikhov

Nesmeyanov Institute of Organoelement Compounds; Razuvaev Institute of Organometallic Chemistry

Email: trif@iomc.ras.ru
Russian Federation, Moscow; Nizhny Novgorod

Yu. V. Nelyubina

Nesmeyanov Institute of Organoelement Compounds

Email: trif@iomc.ras.ru
Russian Federation, Moscow

A. A. Trifonov

Nesmeyanov Institute of Organoelement Compounds

Author for correspondence.
Email: trif@iomc.ras.ru
Russian Federation, Moscow

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