834884-79-6Relevant articles and documents
Hydrosilylation of RN=CH Imino-Substituted Pyridines without a Catalyst
Novák, Miroslav,Ho?nová, Hana,Dostál, Libor,Glowacki, Britta,Jurkschat, Klaus,Ly?ka, Antonín,Ruzickova, Zdenka,Jambor, Roman
supporting information, p. 3074 - 3083 (2017/03/13)
Treatment of the neutral pyridine-based ligands L1–L3, bearing either one or two RN=CH imine moieties {where L1 and L2 are N,N-chelating ligands 2-(RN=CH)C5H4N (R=Ph (L1) or R=2,4,6-Ph3C6H2 (L2)) and L3 is the N,N,N-chelating ligand 2,6-(RN=CH)2C5H3N (R=2,6-iPr2C6H3)}, with HSiCl3 yielded 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 L3 with an excess of HSiCl3 provided 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 SiHCl3 has also been studied. The experimental work is supplemented by DFT calculations.
