Substituent effects in thermal reactions of a silene with silyl-substituted alkynes: A theoretical study

Hiromasa Tanaka, Yoshihito Shiota, Kazunori Hori, Akinobu Naka, Mitsuo Ishikawa, Kazunari Yoshizawa

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Thermal reactions of a silene derivative (Me 3Si) 2Si=C(OSiMe 3)(t-Bu) (1) with silyl-substituted acetylenes, bis(trimethylsilyl)butadiyne, tert-butyldimethylsilylacetylene, and bis(trimethylsilyl)acetylene have been investigated with density functional theory calculations for the understanding of substituent effects in the reactivity of the silene. The first critical reaction step for determining the final product is the formation of a biradical intermediate from 1 and the acetylenes. A stepwise [2 + 2] cycloaddition via the biradical intermediate gives a silacyclobutene derivative, which is the precursor of the final product. The activation energy for this reaction step as well as thermodynamic stability of the biradical intermediate is governed by an interplay between geometric and electronic factors. The biradical intermediate is destabilized by steric hindrance between bulky substituents on 1 and acetylene, while it can be stabilized by delocalization of an unpaired electron in the acetylene moiety. Silacyclobutene derivatives undergo Si-C bond cleavage to give silabutadiene derivatives. The second critical reaction step is the attack of the OSiMe 3 group on the silene Si atom in the silabutadienes. If the substituent on one of the acetylene C atoms does not easily migrate, the SiMe 3 group of the OSiMe 3 group rebounds to the silene C atom to form an oxasilacyclopentene derivative. If this substituent migrates easily, on the other hand, it migrates to the silene C atom with a simultaneous migration of the OSiMe 3 group, resulting in the formation of an allene derivative.

Original languageEnglish
Pages (from-to)4737-4747
Number of pages11
JournalOrganometallics
Volume31
Issue number13
DOIs
Publication statusPublished - Jul 9 2012

Fingerprint

Alkynes
alkynes
acetylene
Acetylene
Derivatives
Atoms
atoms
Cycloaddition
cycloaddition
products
attack
Density functional theory
Hot Temperature
cleavage
Thermodynamic stability
reactivity
Activation energy
activation energy
density functional theory
thermodynamics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Substituent effects in thermal reactions of a silene with silyl-substituted alkynes : A theoretical study. / Tanaka, Hiromasa; Shiota, Yoshihito; Hori, Kazunori; Naka, Akinobu; Ishikawa, Mitsuo; Yoshizawa, Kazunari.

In: Organometallics, Vol. 31, No. 13, 09.07.2012, p. 4737-4747.

Research output: Contribution to journalArticle

Tanaka, Hiromasa ; Shiota, Yoshihito ; Hori, Kazunori ; Naka, Akinobu ; Ishikawa, Mitsuo ; Yoshizawa, Kazunari. / Substituent effects in thermal reactions of a silene with silyl-substituted alkynes : A theoretical study. In: Organometallics. 2012 ; Vol. 31, No. 13. pp. 4737-4747.
@article{04e2ad807cc844b59dbfe4ea800098b6,
title = "Substituent effects in thermal reactions of a silene with silyl-substituted alkynes: A theoretical study",
abstract = "Thermal reactions of a silene derivative (Me 3Si) 2Si=C(OSiMe 3)(t-Bu) (1) with silyl-substituted acetylenes, bis(trimethylsilyl)butadiyne, tert-butyldimethylsilylacetylene, and bis(trimethylsilyl)acetylene have been investigated with density functional theory calculations for the understanding of substituent effects in the reactivity of the silene. The first critical reaction step for determining the final product is the formation of a biradical intermediate from 1 and the acetylenes. A stepwise [2 + 2] cycloaddition via the biradical intermediate gives a silacyclobutene derivative, which is the precursor of the final product. The activation energy for this reaction step as well as thermodynamic stability of the biradical intermediate is governed by an interplay between geometric and electronic factors. The biradical intermediate is destabilized by steric hindrance between bulky substituents on 1 and acetylene, while it can be stabilized by delocalization of an unpaired electron in the acetylene moiety. Silacyclobutene derivatives undergo Si-C bond cleavage to give silabutadiene derivatives. The second critical reaction step is the attack of the OSiMe 3 group on the silene Si atom in the silabutadienes. If the substituent on one of the acetylene C atoms does not easily migrate, the SiMe 3 group of the OSiMe 3 group rebounds to the silene C atom to form an oxasilacyclopentene derivative. If this substituent migrates easily, on the other hand, it migrates to the silene C atom with a simultaneous migration of the OSiMe 3 group, resulting in the formation of an allene derivative.",
author = "Hiromasa Tanaka and Yoshihito Shiota and Kazunori Hori and Akinobu Naka and Mitsuo Ishikawa and Kazunari Yoshizawa",
year = "2012",
month = "7",
day = "9",
doi = "10.1021/om300310g",
language = "English",
volume = "31",
pages = "4737--4747",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Substituent effects in thermal reactions of a silene with silyl-substituted alkynes

T2 - A theoretical study

AU - Tanaka, Hiromasa

AU - Shiota, Yoshihito

AU - Hori, Kazunori

AU - Naka, Akinobu

AU - Ishikawa, Mitsuo

AU - Yoshizawa, Kazunari

PY - 2012/7/9

Y1 - 2012/7/9

N2 - Thermal reactions of a silene derivative (Me 3Si) 2Si=C(OSiMe 3)(t-Bu) (1) with silyl-substituted acetylenes, bis(trimethylsilyl)butadiyne, tert-butyldimethylsilylacetylene, and bis(trimethylsilyl)acetylene have been investigated with density functional theory calculations for the understanding of substituent effects in the reactivity of the silene. The first critical reaction step for determining the final product is the formation of a biradical intermediate from 1 and the acetylenes. A stepwise [2 + 2] cycloaddition via the biradical intermediate gives a silacyclobutene derivative, which is the precursor of the final product. The activation energy for this reaction step as well as thermodynamic stability of the biradical intermediate is governed by an interplay between geometric and electronic factors. The biradical intermediate is destabilized by steric hindrance between bulky substituents on 1 and acetylene, while it can be stabilized by delocalization of an unpaired electron in the acetylene moiety. Silacyclobutene derivatives undergo Si-C bond cleavage to give silabutadiene derivatives. The second critical reaction step is the attack of the OSiMe 3 group on the silene Si atom in the silabutadienes. If the substituent on one of the acetylene C atoms does not easily migrate, the SiMe 3 group of the OSiMe 3 group rebounds to the silene C atom to form an oxasilacyclopentene derivative. If this substituent migrates easily, on the other hand, it migrates to the silene C atom with a simultaneous migration of the OSiMe 3 group, resulting in the formation of an allene derivative.

AB - Thermal reactions of a silene derivative (Me 3Si) 2Si=C(OSiMe 3)(t-Bu) (1) with silyl-substituted acetylenes, bis(trimethylsilyl)butadiyne, tert-butyldimethylsilylacetylene, and bis(trimethylsilyl)acetylene have been investigated with density functional theory calculations for the understanding of substituent effects in the reactivity of the silene. The first critical reaction step for determining the final product is the formation of a biradical intermediate from 1 and the acetylenes. A stepwise [2 + 2] cycloaddition via the biradical intermediate gives a silacyclobutene derivative, which is the precursor of the final product. The activation energy for this reaction step as well as thermodynamic stability of the biradical intermediate is governed by an interplay between geometric and electronic factors. The biradical intermediate is destabilized by steric hindrance between bulky substituents on 1 and acetylene, while it can be stabilized by delocalization of an unpaired electron in the acetylene moiety. Silacyclobutene derivatives undergo Si-C bond cleavage to give silabutadiene derivatives. The second critical reaction step is the attack of the OSiMe 3 group on the silene Si atom in the silabutadienes. If the substituent on one of the acetylene C atoms does not easily migrate, the SiMe 3 group of the OSiMe 3 group rebounds to the silene C atom to form an oxasilacyclopentene derivative. If this substituent migrates easily, on the other hand, it migrates to the silene C atom with a simultaneous migration of the OSiMe 3 group, resulting in the formation of an allene derivative.

UR - http://www.scopus.com/inward/record.url?scp=84863697858&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84863697858&partnerID=8YFLogxK

U2 - 10.1021/om300310g

DO - 10.1021/om300310g

M3 - Article

AN - SCOPUS:84863697858

VL - 31

SP - 4737

EP - 4747

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 13

ER -