RESUMO
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)C5 H4 N (R=Ph (L1 ) or R=2,4,6-Ph3 C6 H2 (L2 )) and L3 is the N,N,N-chelating ligand 2,6-(RN=CH)2 C5 H3 N (R=2,6-iPr2 C6 H3 )}, with HSiCl3 yielded NâSi-coordinated silicon(IV) amides 2-{Cl3 SiN(R)CH2 }C5 H4 N (1, R=Ph; 2, R=2,4,6-Ph3 C6 H2 ) and 2-{Cl3 SiN(R)CH2 }-6-(RN=CH)C5 H4 N (3, R=2,6-iPr2 C6 H3 ). The organosilicon amides 1-3 are the products of spontaneous hydrosilylation of the RN=CH imine moiety induced by NâSi coordination of the proposed N,N-chelated chlorosilanes L1 âSiHCl3 (1 a), L2 âSiHCl3 (2 a), and L3 âSiHCl3 (3 a). Furthermore, the reaction of L3 with an excess of HSiCl3 provided the intramolecularly coordinated chlorosilicon diamide cyclo-{(C5 H3 N)-1,3-(CH2 NR)2 }SiCl2 (4) (R=2,6-iPr2 C6 H3 ) 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.