Mediation of substituent effects via monoatomic SiMe2, CMe2 and CH2 σ-spacers. An NMR investigation.

Cornelis A. Van Walree; Leonardus W. Jenneskens

doi:10.1016/S0040-4020(97)00241-X

Mediation of substituent effects via monoatomic SiMe2, CMe2 and CH2 σ-spacers. An NMR investigation.

Cornelis A. Van Walree, Leonardus W. Jenneskens

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Abstract

The ability of the monoatomic σ-spacers SiMe2, CMe2 and CH2 to mediate substituent effects in 4-mono- and 1,4-bissubstituted dimethyldiphenylsilanes 1-2. 2,2-diphenylpropanes 3-4 and diphenylmethones 5-6, respectively, has been studied with NMR spectroscopy. From Hammett plots between either 29Si or 13C NMR chemical shifts vs. Hammett substituent constants σ(p) it is concluded that the enhanced ability of the SiMe2 σ-spacer to mediate substituent effects has to be attributed to the larger polarizability of Si-C bonds relative to C-C bonds.

Original language	English
Pages (from-to)	5825-5830
Number of pages	6
Journal	Tetrahedron
Volume	53
Issue number	16
DOIs	https://doi.org/10.1016/S0040-4020(97)00241-X
Publication status	Published - 21 Apr 1997

Keywords

silane derivative
article
drug structure
molecular dynamics
nuclear magnetic resonance spectroscopy
priority journal
quantum chemistry

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10.1016/S0040-4020(97)00241-X

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title = "Mediation of substituent effects via monoatomic SiMe2, CMe2 and CH2 σ-spacers. An NMR investigation.",

abstract = "The ability of the monoatomic σ-spacers SiMe2, CMe2 and CH2 to mediate substituent effects in 4-mono- and 1,4-bissubstituted dimethyldiphenylsilanes 1-2. 2,2-diphenylpropanes 3-4 and diphenylmethones 5-6, respectively, has been studied with NMR spectroscopy. From Hammett plots between either 29Si or 13C NMR chemical shifts vs. Hammett substituent constants σ(p) it is concluded that the enhanced ability of the SiMe2 σ-spacer to mediate substituent effects has to be attributed to the larger polarizability of Si-C bonds relative to C-C bonds.",

keywords = "silane derivative, article, drug structure, molecular dynamics, nuclear magnetic resonance spectroscopy, priority journal, quantum chemistry",

author = "{Van Walree}, {Cornelis A.} and Jenneskens, {Leonardus W.}",

year = "1997",

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doi = "10.1016/S0040-4020(97)00241-X",

language = "English",

volume = "53",

pages = "5825--5830",

journal = "Tetrahedron",

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TY - JOUR

T1 - Mediation of substituent effects via monoatomic SiMe2, CMe2 and CH2 σ-spacers. An NMR investigation.

AU - Van Walree, Cornelis A.

AU - Jenneskens, Leonardus W.

PY - 1997/4/21

Y1 - 1997/4/21

N2 - The ability of the monoatomic σ-spacers SiMe2, CMe2 and CH2 to mediate substituent effects in 4-mono- and 1,4-bissubstituted dimethyldiphenylsilanes 1-2. 2,2-diphenylpropanes 3-4 and diphenylmethones 5-6, respectively, has been studied with NMR spectroscopy. From Hammett plots between either 29Si or 13C NMR chemical shifts vs. Hammett substituent constants σ(p) it is concluded that the enhanced ability of the SiMe2 σ-spacer to mediate substituent effects has to be attributed to the larger polarizability of Si-C bonds relative to C-C bonds.

AB - The ability of the monoatomic σ-spacers SiMe2, CMe2 and CH2 to mediate substituent effects in 4-mono- and 1,4-bissubstituted dimethyldiphenylsilanes 1-2. 2,2-diphenylpropanes 3-4 and diphenylmethones 5-6, respectively, has been studied with NMR spectroscopy. From Hammett plots between either 29Si or 13C NMR chemical shifts vs. Hammett substituent constants σ(p) it is concluded that the enhanced ability of the SiMe2 σ-spacer to mediate substituent effects has to be attributed to the larger polarizability of Si-C bonds relative to C-C bonds.

KW - silane derivative

KW - article

KW - drug structure

KW - molecular dynamics

KW - nuclear magnetic resonance spectroscopy

KW - priority journal

KW - quantum chemistry

U2 - 10.1016/S0040-4020(97)00241-X

DO - 10.1016/S0040-4020(97)00241-X

M3 - Article

SN - 0040-4020

VL - 53

SP - 5825

EP - 5830

JO - Tetrahedron

JF - Tetrahedron

IS - 16

ER -

Mediation of substituent effects via monoatomic SiMe2, CMe2 and CH2 σ-spacers. An NMR investigation.

Abstract

Keywords

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