. "I, P(GA13-00289S)" . . "RIV/00216275:25310/14:39898815!RIV15-MSM-25310___" . . "Our attempts to synthesize the NSi intramolecularly coordinated organosilanes (Ph2LSiH)-Si-1 (1a), (PhLSiH2)-Si-1 (2a), (Ph2LSiH)-Si-2 (3a), and (PhLSiH2)-Si-2 (4a) containing a CHN imine group (in which L-1 is the C,N-chelating ligand {2-[CHN(C6H3-2,6-iPr(2))]C6H4}(-) and L-2 is {2-[CHN(tBu)]C6H4}(-)) yielded 1-[2,6-bis(diisopropyl)phenyl]-2,2-diphenyl-1-aza-silole (1), 1-[2,6-bis(diisopropyl)phenyl]-2-phenyl-2-hydrido-1-aza-silole (2), 1-tert-butyl-2,2-diphenyl-1-aza-silole (3), and 1-tert-butyl-2-phenyl-2-hydrido-1-aza-silole (4), respectively. Isolated organosilicon amides 1-4 are an outcome of the spontaneous hydrosilylation of the CHN imine moiety induced by NSi intramolecular coordination. Compounds 1-4 were characterized by NMR spectroscopy and X-ray diffraction analysis. The geometries of organosilanes 1a-4a and their corresponding hydrosilylated products 1-4 were optimized and fully characterized at the B3LYP/6-31++G(d,p) level of theory. The molecular structure determination of 1-3 suggested the presence of a SiN double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor-acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the SiN bond is highly polarized pointing to a predominantly zwitterionic Si+N- bond in 1-4. Since compounds 1-4 are hydrosilylated products of 1a-4a, the free energies (G(298)), enthalpies (H-298), and entropies (H-298) were computed for the hydrosilylation reaction of 1a-4a with both B3LYP and B3LYP-D methods. On the basis of the very negative G(298) values, the hydrosilylation reaction is highly exergonic and compounds 1a-4a are spontaneously transformed into 1-4 in the absence of a catalyst." . "RIV/00216275:25310/14:39898815" . "4"^^ . "Ly\u010Dka, Anton\u00EDn" . . "20124" . "Jambor, Roman" . "20" . . . . "De Proft, Frank" . . "9" . "[2BD247392C21]" . "Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst" . . "Chemistry - A European Journal" . . "Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst" . "0947-6539" . "7"^^ . "000331729700022" . . "Dost\u00E1l, Libor" . . . "25310" . . "Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst"@en . "10.1002/chem.201303203" . . . "Our attempts to synthesize the NSi intramolecularly coordinated organosilanes (Ph2LSiH)-Si-1 (1a), (PhLSiH2)-Si-1 (2a), (Ph2LSiH)-Si-2 (3a), and (PhLSiH2)-Si-2 (4a) containing a CHN imine group (in which L-1 is the C,N-chelating ligand {2-[CHN(C6H3-2,6-iPr(2))]C6H4}(-) and L-2 is {2-[CHN(tBu)]C6H4}(-)) yielded 1-[2,6-bis(diisopropyl)phenyl]-2,2-diphenyl-1-aza-silole (1), 1-[2,6-bis(diisopropyl)phenyl]-2-phenyl-2-hydrido-1-aza-silole (2), 1-tert-butyl-2,2-diphenyl-1-aza-silole (3), and 1-tert-butyl-2-phenyl-2-hydrido-1-aza-silole (4), respectively. Isolated organosilicon amides 1-4 are an outcome of the spontaneous hydrosilylation of the CHN imine moiety induced by NSi intramolecular coordination. Compounds 1-4 were characterized by NMR spectroscopy and X-ray diffraction analysis. The geometries of organosilanes 1a-4a and their corresponding hydrosilylated products 1-4 were optimized and fully characterized at the B3LYP/6-31++G(d,p) level of theory. The molecular structure determination of 1-3 suggested the presence of a SiN double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor-acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the SiN bond is highly polarized pointing to a predominantly zwitterionic Si+N- bond in 1-4. Since compounds 1-4 are hydrosilylated products of 1a-4a, the free energies (G(298)), enthalpies (H-298), and entropies (H-298) were computed for the hydrosilylation reaction of 1a-4a with both B3LYP and B3LYP-D methods. On the basis of the very negative G(298) values, the hydrosilylation reaction is highly exergonic and compounds 1a-4a are spontaneously transformed into 1-4 in the absence of a catalyst."@en . "DE - Spolkov\u00E1 republika N\u011Bmecko" . "Nov\u00E1k, Miroslav" . . "Catalyst; Absence; the; Molecules; SiloleType; 1-Aza-; into; Organosilanes; Transformation; Spontaneous; Coordination; Intramolecular; Induced; Hydrosilylation"@en . . "R\u016F\u017Ei\u010Dka, Ale\u0161" . . "Alonso, Mercedes" . . . . . . . . "9"^^ . . . . "Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst"@en . .