Attempted stabilization of silaethylenes with aryl or trifluoromethyl groups

Brook, A. G.; Krishna, R.; Kallury, M. R.; Poon, Y. C.

doi:10.1021/om00067a017

Cited by 23 publications

(4 citation statements)

References 3 publications

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“…With the bulkier R CEt 3 and 1-Ad groups, no silene dimers were formed. A phenyl substituent at the C atom, on the other hand, did not provide the same stabilization as a bulky alkyl group despite the possible conjugative stabilization, and only dimers 73g were detected [120]. A p-methoxyphenyl substituent did not significantly improve the stability of the silene when compared to the phenyl substituent.…”

Section: Dimerization Aptitudementioning

confidence: 84%

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Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Ottosson

Eklöf

2008

Coordination Chemistry Reviews

137

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Section: Dimerization Aptitudementioning

confidence: 84%

“…Interestingly, Brook-type silenes with R CF 3 dimerized to give the cis-isomer 73j of the 1,2-disilacyclobutane in addition to the trans-isomer observed in the dimerization of the other (Me 3 Si) 2 Si C(OSiMe 3 )R silenes [120].…”

Section: Dimerization Aptitudementioning

confidence: 99%

Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Ottosson

Eklöf

2008

Coordination Chemistry Reviews

137

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“…Thus, δ( 29 Si) varies from 34.3 ppm for the 2-siloxysilene (Me 3 Si) 2 SiC(OSiEt 3 )Mes ( 9 ) 24 to 144.2 ppm for the silene Me 2 SiC(SiMe 3 )SiMe(t-Bu) 2 ( 10 ) . The 13 C chemical shift data cover an even wider range: while the doubly bonded carbon in the siloxysilene (Me 3 Si) 2 SiC(OSiMe 3 ) 1 Ad ( 11 ; 1 Ad = 1-adamantyl) resonates at 214.2 ppm, this signal appears at only 77.2 ppm in the 13 C NMR spectrum of 10 . To obtain reliable information about NMR chemical shifts of small silenes such as 2 , 7 , and 8 and their complexes with dimethyl ether, quantum-mechanical calculations of the geometries and magnetic properties were performed.…”

Section: Resultsmentioning

confidence: 99%

Transient Silenes and Their Dimethyl-d₆ Ether Donor Complexes from the Gas-Phase Pyrolysis of Siletanes^,

et al. 2000

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The silenes H 2 SidCH 2 (2), MeHSidCH 2 (7), and Me 2 SidCH 2 (8) have been prepared by low-pressure flow pyrolysis from the corresponding siletanes H 2 SiCH 2 CH 2 CH 2 (1), MeHSiCH 2 -CH 2 CH 2 (5), and Me 2 SiCH 2 CH 2 CH 2 (6). 2, 7, and 8 were identified by residual gas analysis of the pyrolysis stream and by low-temperature NMR spectroscopy of their complexes 2‚ O(CD 3 ) 2 ( 16), 7‚O(CD 3 ) 2 ( 17), and 8‚O(CD 3 ) 2 ( 18). The complexes 16-18 are stable to temperatures between -140 and -100 °C. Above these temperatures rapid polymerization occurs. The complexation with dimethyl ether obviously stabilizes the silenes and allows their spectroscopic investigation. The 29 Si chemical shifts of the complexes are -25.2 (16), -1.8 (17) and 16.8 ppm ( 18). The experimental results are supported by ab initio and density functional calculations of geometries and magnetic properties of the silenes 2, 7, and 8 and the dimethyl ether complexes 16-18. The calculations predict a relatively short Si-O separation of about 1.7 Å in the corresponding silene-ether adducts. Natural bond analysis of the donor-acceptor complex 16 reveals that the interaction between the ether molecule and the silene is predominantly ionic, despite the relatively short Si-O distance.

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“…The quest for a stable CSi double‐bond compounds and the study of their related chemical reactions has been a focus of attention for chemists for many decades. Brook et al 27,28 have succeed for the first time to isolate stable silenes of the general formula (Me 3 SiO)RCSi(Me 3 Si 2 ). Apeloig et al 29,30 have showed that σ‐donor or π‐acceptor substituents at silicon, and/or σ‐acceptor or π‐donor substituents at carbon, which lead to increased kinetic stability, have the effect of reducing the natural ( δ− CSi δ+ ) polarity of the bond relative to that in the parent molecule.…”

Section: Introductionmentioning

confidence: 99%

The competition and cooperativity of hydrogen/halogen bond and π‐hole bond involving the heteronuclear ethylene analogues

et al. 2021

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The noncovalent interactions involving heteronuclear ethylene analogues H2CEH2 (E = Si, Ge and Sn) have been studied by the Møller–Plesset perturbation theory to investigate the competition and cooperativity between the hydrogen/halogen bond and π‐hole bond. H2CEH2 has a dual role of being a Lewis base and acid with the region of π‐electron accumulation above the carbon atom and the region of π‐electron depletion (π‐hole) above the E atom to participate in the NCX···CE (X = H and Cl) hydrogen/halogen bond and CE···NCY (Y = H, Cl, Li and Na) π‐hole bond, respectively. When HCN/ClCN interacts with H2CEH2 by two sites, the strength of hydrogen bond/halogen bond is stronger than that of π‐hole bond. The π‐hole bond becomes obviously stronger when the metal substituent of YCN (Y = Li and Na) interacting with H2CEH2, showing the character of partial covalent, its strength is much greater than that of hydrogen/halogen bond. In the ternary complexes, both hydrogen/halogen bond and π‐hole bond are simultaneously strengthened compared to those in the binary complexes, especially in the systems containing alkali metal.

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Attempted stabilization of silaethylenes with aryl or trifluoromethyl groups

Cited by 23 publications

References 3 publications

Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Transient Silenes and Their Dimethyl-d₆ Ether Donor Complexes from the Gas-Phase Pyrolysis of Siletanes^,

The competition and cooperativity of hydrogen/halogen bond and π‐hole bond involving the heteronuclear ethylene analogues

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Attempted stabilization of silaethylenes with aryl or trifluoromethyl groups

Cited by 23 publications

References 3 publications

Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Silenes: Connectors between classical alkenes and nonclassical heavy alkenes

Transient Silenes and Their Dimethyl-d6 Ether Donor Complexes from the Gas-Phase Pyrolysis of Siletanes,

The competition and cooperativity of hydrogen/halogen bond and π‐hole bond involving the heteronuclear ethylene analogues

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Product

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Transient Silenes and Their Dimethyl-d₆ Ether Donor Complexes from the Gas-Phase Pyrolysis of Siletanes^,