Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

Hiroyuki Sakaba; Hiroyuki Oike; Yasuhiro Arai; Eunsang Kwon

doi:10.1021/om300772c

Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

Hiroyuki Sakaba, Hiroyuki Oike, Yasuhiro Arai, Eunsang Kwon

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

Reaction of acetylide-silylene complex Cp*(CO)₂W(SiPh ₂)(CC^tBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*(CO)₂W(SiPh₂·DMAP)(CC ^tBu) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)₂W(SiPh₂)(CCSiMe₃) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)₂W[CC(SiPh₂·DMAP)(SiMe₃)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)₂W(SiPh₂·DMAP)(CCSiMe ₃) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)₂W(SiPh ₂·py)(CCSiMe₃) (trans-5b and cis-5b) and Cp*(CO)₂W[CC(SiPh₂·py)(SiMe₃)] (6b) at low temperature, while a mixture of 1a and pyridine showed no such spectral changes.

Original language	English
Pages (from-to)	8172-8177
Number of pages	6
Journal	Organometallics
Volume	31
Issue number	23
DOIs	https://doi.org/10.1021/om300772c
Publication status	Published - 2012 Dec 10

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Reactions of tungsten acetylide-silylene complexes with pyridines : Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks. / Sakaba, Hiroyuki; Oike, Hiroyuki; Arai, Yasuhiro; Kwon, Eunsang.

In: Organometallics, Vol. 31, No. 23, 10.12.2012, p. 8172-8177.

Research output: Contribution to journal › Article › peer-review

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title = "Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks",

abstract = "Reaction of acetylide-silylene complex Cp*(CO)2W(SiPh 2)(CCtBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CC tBu) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)2W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe 3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)2W(SiPh 2·py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b) at low temperature, while a mixture of 1a and pyridine showed no such spectral changes.",

author = "Hiroyuki Sakaba and Hiroyuki Oike and Yasuhiro Arai and Eunsang Kwon",

year = "2012",

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doi = "10.1021/om300772c",

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T1 - Reactions of tungsten acetylide-silylene complexes with pyridines

T2 - Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

AU - Sakaba, Hiroyuki

AU - Oike, Hiroyuki

AU - Arai, Yasuhiro

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N2 - Reaction of acetylide-silylene complex Cp*(CO)2W(SiPh 2)(CCtBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CC tBu) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)2W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe 3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)2W(SiPh 2·py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b) at low temperature, while a mixture of 1a and pyridine showed no such spectral changes.

AB - Reaction of acetylide-silylene complex Cp*(CO)2W(SiPh 2)(CCtBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CC tBu) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)2W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe 3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)2W(SiPh 2·py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b) at low temperature, while a mixture of 1a and pyridine showed no such spectral changes.

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Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

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