NHC-induced conversion of a W–Ge double bond into the triple bond through formation of W–Ge single and double bonded intermediates

Tetsuya Fukuda; Hisako Hashimoto; Hiromi Tobita

doi:10.1016/j.jorganchem.2017.07.027

NHC-induced conversion of a W–Ge double bond into the triple bond through formation of W–Ge single and double bonded intermediates

Tetsuya Fukuda, Hisako Hashimoto, Hiromi Tobita

SCI - Chemistry

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

5 Citations (Scopus)

Abstract

Reaction of hydrido(hydrogermylene) complex Cp*(CO)₂(H)W=Ge(H)(Tsi) (1, Tsi = C(SiMe₃)₃) with 1 equiv of ^MeIMe (^MeIMe = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) immediately afforded NHC-stabilized germylene complex Cp*(CO)₂(H)WGe(H)(^MeIMe)(Tsi) (2) that has a zwitterionic, W–Ge single-bonded structure. Complex 2 was thermally unstable and intramolecular proton-transfer followed by hydride-transfer to the NHC-unit occurred slowly at room temperature to give anionic germylene complex [Cp*(CO)₂W=Ge(H)(Tsi)][H^MeIMe] ([3][H^MeIMe]) first and subsequently germylyne complex Cp*(CO)₂W≡Ge(Tsi) (4) and H₂^MeIMe. Although [3][H^MeIMe] was too unstable to be isolated, the salt of bulkier [H^MeIⁱPr]⁺, [Cp*(CO)₂W=Ge(H)(Tsi)][H^MeIⁱPr] ([3][H^MeIⁱPr]), was thermally more stable and was isolated and fully characterized.

Original language	English
Pages (from-to)	89-94
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	848
DOIs	https://doi.org/10.1016/j.jorganchem.2017.07.027
Publication status	Published - 2017 Jan 1

Keywords

Germylene complex
Germylyne complex
Hydride transfer
NHC-carbene
Proton transfer
X-ray diffraction

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{7fb80faced10419b814d125a84ca28f7,

title = "NHC-induced conversion of a W–Ge double bond into the triple bond through formation of W–Ge single and double bonded intermediates",

abstract = "Reaction of hydrido(hydrogermylene) complex Cp*(CO)2(H)W=Ge(H)(Tsi) (1, Tsi = C(SiMe3)3) with 1 equiv of MeIMe (MeIMe = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) immediately afforded NHC-stabilized germylene complex Cp*(CO)2(H)WGe(H)(MeIMe)(Tsi) (2) that has a zwitterionic, W–Ge single-bonded structure. Complex 2 was thermally unstable and intramolecular proton-transfer followed by hydride-transfer to the NHC-unit occurred slowly at room temperature to give anionic germylene complex [Cp*(CO)2W=Ge(H)(Tsi)][HMeIMe] ([3][HMeIMe]) first and subsequently germylyne complex Cp*(CO)2W≡Ge(Tsi) (4) and H2MeIMe. Although [3][HMeIMe] was too unstable to be isolated, the salt of bulkier [HMeIiPr]+, [Cp*(CO)2W=Ge(H)(Tsi)][HMeIiPr] ([3][HMeIiPr]), was thermally more stable and was isolated and fully characterized.",

keywords = "Germylene complex, Germylyne complex, Hydride transfer, NHC-carbene, Proton transfer, X-ray diffraction",

author = "Tetsuya Fukuda and Hisako Hashimoto and Hiromi Tobita",

year = "2017",

month = jan,

day = "1",

doi = "10.1016/j.jorganchem.2017.07.027",

language = "English",

volume = "848",

pages = "89--94",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

}

TY - JOUR

T1 - NHC-induced conversion of a W–Ge double bond into the triple bond through formation of W–Ge single and double bonded intermediates

AU - Fukuda, Tetsuya

AU - Hashimoto, Hisako

AU - Tobita, Hiromi

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Reaction of hydrido(hydrogermylene) complex Cp*(CO)2(H)W=Ge(H)(Tsi) (1, Tsi = C(SiMe3)3) with 1 equiv of MeIMe (MeIMe = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) immediately afforded NHC-stabilized germylene complex Cp*(CO)2(H)WGe(H)(MeIMe)(Tsi) (2) that has a zwitterionic, W–Ge single-bonded structure. Complex 2 was thermally unstable and intramolecular proton-transfer followed by hydride-transfer to the NHC-unit occurred slowly at room temperature to give anionic germylene complex [Cp*(CO)2W=Ge(H)(Tsi)][HMeIMe] ([3][HMeIMe]) first and subsequently germylyne complex Cp*(CO)2W≡Ge(Tsi) (4) and H2MeIMe. Although [3][HMeIMe] was too unstable to be isolated, the salt of bulkier [HMeIiPr]+, [Cp*(CO)2W=Ge(H)(Tsi)][HMeIiPr] ([3][HMeIiPr]), was thermally more stable and was isolated and fully characterized.

AB - Reaction of hydrido(hydrogermylene) complex Cp*(CO)2(H)W=Ge(H)(Tsi) (1, Tsi = C(SiMe3)3) with 1 equiv of MeIMe (MeIMe = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) immediately afforded NHC-stabilized germylene complex Cp*(CO)2(H)WGe(H)(MeIMe)(Tsi) (2) that has a zwitterionic, W–Ge single-bonded structure. Complex 2 was thermally unstable and intramolecular proton-transfer followed by hydride-transfer to the NHC-unit occurred slowly at room temperature to give anionic germylene complex [Cp*(CO)2W=Ge(H)(Tsi)][HMeIMe] ([3][HMeIMe]) first and subsequently germylyne complex Cp*(CO)2W≡Ge(Tsi) (4) and H2MeIMe. Although [3][HMeIMe] was too unstable to be isolated, the salt of bulkier [HMeIiPr]+, [Cp*(CO)2W=Ge(H)(Tsi)][HMeIiPr] ([3][HMeIiPr]), was thermally more stable and was isolated and fully characterized.

KW - Germylene complex

KW - Germylyne complex

KW - Hydride transfer

KW - NHC-carbene

KW - Proton transfer

KW - X-ray diffraction

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U2 - 10.1016/j.jorganchem.2017.07.027

DO - 10.1016/j.jorganchem.2017.07.027

M3 - Article

AN - SCOPUS:85026371622

VL - 848

SP - 89

EP - 94

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -