title: Hydrosilylation of RN=CH Imino-Substituted Pyridines without a Catalyst.
abstract: Treatment of the neutral pyridine-based ligands L1-L3, bearing either one or two RN=CH imine moieties {where L1and L2are N,N-chelating ligands 2-(RN=CH)C5H4N (R=Ph (L1) or R=2,4,6-Ph3C6H2(L2)) and L3is the N,N,N-chelating ligand 2,6-(RN=CH)2C5H3N (R=2,6-iPr2C6H3)}, with HSiCl3yielded N→Si-coordinated silicon(IV) amides 2-{Cl3SiN(R)CH2}C5H4N (1, R=Ph; 2, R=2,4,6-Ph3C6H2) and 2-{Cl3SiN(R)CH2}-6-(RN=CH)C5H4N (3, R=2,6-iPr2C6H3). The organosilicon amides 1-3 are the products of spontaneous hydrosilylation of the RN=CH imine moiety induced by N→Si coordination of the proposed N,N-chelated chlorosilanes L1→SiHCl3(1 a), L2→SiHCl3(2 a), and L3→SiHCl3(3 a). Furthermore, the reaction of L3with an excess of HSiCl3provided the intramolecularly coordinated chlorosilicon diamide cyclo-{(C5H3N)-1,3-(CH2NR)2}SiCl2(4) (R=2,6-iPr2C6H3) as the product of spontaneous reduction of both RN=CH imine moieties. The compounds have been characterized by NMR spectroscopy (1-4) and single-crystal X-ray diffraction analysis (1, 3, and 4). The mechanism of the hydrosilylation of the second RN=CH imine moiety in 3 by an excess of SiHCl3has also been studied. The experimental work is supplemented by DFT calculations.
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Miroslav
authors.initials: M
authors.lastname: Novák
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Hana
authors.initials: H
authors.lastname: Hošnová
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Libor
authors.initials: L
authors.lastname: Dostál
authors.affiliation: Fakultät für Chemie und Chemische Biologie, Technische Universität, 44227, Dortmund, Germany.
authors.forename: Britta
authors.initials: B
authors.lastname: Glowacki
authors.affiliation: Fakultät für Chemie und Chemische Biologie, Technische Universität, 44227, Dortmund, Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Jurkschat
authors.affiliation: Centre of Organic Chemistry, Rybitví 296, 53354, Rybitví, Czech Republic.
authors.forename: Antonín
authors.initials: A
authors.lastname: Lyčka
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Zdenka
authors.initials: Z
authors.lastname: Ruzickova
authors.affiliation: Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice, Czech Republic.
authors.forename: Roman
authors.initials: R
authors.lastname: Jambor
keywords: NMR spectroscopy; density functional calculations; hydrosilylation; intramolecular coordination; silicon