Treatment of the neutral pyridine-based ligands L -L , bearing either one or two RN=CH imine moieties {where L and L are N,N-chelating ligands 2-(RN=CH)C H N (R=Ph (L ) or R=2,4,6-Ph C H (L )) and L is the N,N,N-chelating ligand 2,6-(RN=CH) C H N (R=2,6-iPr C H )}, with HSiCl yielded N→Si-coordinated silicon(IV) amides 2-{Cl SiN(R)CH }C H N (1, R=Ph; 2, R=2,4,6-Ph C H ) and 2-{Cl SiN(R)CH }-6-(RN=CH)C H N (3, R=2,6-iPr C H ). 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 L →SiHCl (1 a), L →SiHCl (2 a), and L →SiHCl (3 a). Furthermore, the reaction of L with an excess of HSiCl provided the intramolecularly coordinated chlorosilicon diamide cyclo-{(C H N)-1,3-(CH NR) }SiCl (4) (R=2,6-iPr C H ) 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 SiHCl has also been studied. The experimental work is supplemented by DFT calculations.

No abstract