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
N1 - Funding Information:
This work was supported by the Ministry of Education, Culture, Sports, Science and Technology, Japan (Grants-in-aid for Scientific Research Nos. JP15H03782, JPK05444, and JP25?1537) and a Grant-in-Aid for Scientific Research on Innovative Areas, ?Stimuli-responsive Chemical Species for the Creation of Functional Molecules? [#2408] (JSPS KAKENHI Grant Number No. JP24109011), and JSPS Research Fellowships for Young Scientists (T. F.).
Publisher Copyright:
© 2017 Elsevier B.V.
PY - 2017
Y1 - 2017
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 -