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Statements

Subject Item
n2:RIV%2F00216275%3A25310%2F14%3A39898815%21RIV15-MSM-25310___
rdf:type
n11:Vysledek skos:Concept
dcterms: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.
dcterms: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
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
skos:notation
RIV/00216275:25310/14:39898815!RIV15-MSM-25310___
n3:aktivita
n16:P n16:I
n3:aktivity
I, P(GA13-00289S)
n3:cisloPeriodika
9
n3:dodaniDat
n6:2015
n3:domaciTvurceVysledku
n8:8975671 n8:5107962 n8:1403753 n8:4470788
n3:druhVysledku
n18:J
n3:duvernostUdaju
n13:S
n3:entitaPredkladatele
n9:predkladatel
n3:idSjednocenehoVysledku
20124
n3:idVysledku
RIV/00216275:25310/14:39898815
n3:jazykVysledku
n17:eng
n3:klicovaSlova
Catalyst; Absence; the; Molecules; SiloleType; 1-Aza-; into; Organosilanes; Transformation; Spontaneous; Coordination; Intramolecular; Induced; Hydrosilylation
n3:klicoveSlovo
n4:Hydrosilylation n4:Organosilanes n4:Intramolecular n4:Spontaneous n4:Catalyst n4:Transformation n4:1-Aza- n4:Absence n4:Coordination n4:the n4:into n4:SiloleType n4:Molecules n4:Induced
n3:kodStatuVydavatele
DE - Spolková republika Německo
n3:kontrolniKodProRIV
[2BD247392C21]
n3:nazevZdroje
Chemistry - A European Journal
n3:obor
n19:CA
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
7
n3:projekt
n15:GA13-00289S
n3:rokUplatneniVysledku
n6:2014
n3:svazekPeriodika
20
n3:tvurceVysledku
Lyčka, Antonín Jambor, Roman De Proft, Frank Dostál, Libor Novák, Miroslav Růžička, Aleš Alonso, Mercedes
n3:wos
000331729700022
s:issn
0947-6539
s:numberOfPages
9
n14:doi
10.1002/chem.201303203
n12:organizacniJednotka
25310