About: Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	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. 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)
Title	Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst (en)
skos:prefLabel	Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst Hydrosilylation Induced by N! Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1-Aza- SiloleType Molecules in the Absence of a Catalyst (en)
skos:notation	RIV/00216275:25310/14:39898815!RIV15-MSM-25310___
http://linked.open...avai/riv/aktivita	I P
http://linked.open...avai/riv/aktivity	I, P(GA13-00289S)
http://linked.open...iv/cisloPeriodika	9
http://linked.open...vai/riv/dodaniDat	2015
http://linked.open...aciTvurceVysledku	Dostál, Libor Růžička, Aleš Jambor, Roman Novák, Miroslav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Univerzita Pardubice / Fakulta chemicko-technologická
http://linked.open...dnocenehoVysledku	20124
http://linked.open...ai/riv/idVysledku	RIV/00216275:25310/14:39898815
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	Catalyst; Absence; the; Molecules; SiloleType; 1-Aza-; into; Organosilanes; Transformation; Spontaneous; Coordination; Intramolecular; Induced; Hydrosilylation (en)
http://linked.open.../riv/klicoveSlovo	into Induced Molecules Organosilanes Absence Transformation the Catalyst Coordination Hydrosilylation 1-Aza- Intramolecular SiloleType Spontaneous
http://linked.open...odStatuVydavatele	DE - Spolková republika Německo
http://linked.open...ontrolniKodProRIV	[2BD247392C21]
http://linked.open...i/riv/nazevZdroje	Chemistry - A European Journal
http://linked.open...in/vavai/riv/obor	CA
http://linked.open...ichTvurcuVysledku	4 (xsd:int)
http://linked.open...cetTvurcuVysledku	7 (xsd:int)
http://linked.open...vavai/riv/projekt	Heteroboroxines-A New Class of Boroxine Based Compounds
http://linked.open...UplatneniVysledku	2014
http://linked.open...v/svazekPeriodika	20
http://linked.open...iv/tvurceVysledku	Dostál, Libor Jambor, Roman Novák, Miroslav Růžička, Aleš Lyčka, Antonín De Proft, Frank Alonso, Mercedes
http://linked.open...ain/vavai/riv/wos	000331729700022
issn	0947-6539
number of pages	9 (xsd:int)
http://bibframe.org/vocab/doi	10.1002/chem.201303203
http://localhost/t...ganizacniJednotka	25310

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