Tri-tert-butylsilylsilylenes with alkali metal substituents ( tBu3Si)SiM (M = Li, K): Electronically and sterically accessible triplet ground states

Akira Sekiguchi; Takashi Tanaka; Masaaki Ichinohe; Kimio Akiyama; Peter P. Gaspar

doi:10.1021/ja077628v

Tri-tert-butylsilylsilylenes with alkali metal substituents ( ^tBu₃Si)SiM (M = Li, K): Electronically and sterically accessible triplet ground states

Akira Sekiguchi, Takashi Tanaka, Masaaki Ichinohe, Kimio Akiyama, Peter P. Gaspar

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

31 Citations (Scopus)

Abstract

Lithium-, sodium-, and potassium-substituted silirenes 2a-c have been prepared by the reaction of bis(tri-tert-butylsilyl)silirene 1 with the corresponding alkali metals and characterized by NMR spectroscopy and chemical trapping (2a and 2b). Lithio- and potassiosilylenes, Li(^tBu₃Si)₂Si: (4a) and K(^tBu₃Si)₂Si: (4b), were generated by low-temperature irradiation of 2a and 2b, respectively, and their EPR spectra revealed the characteristic broad EPR signals at 790 mT for 4a and 780 mT for 4b. The Curie law dependence observed for 4a was in accord with a triplet ground state, also assigned to 4b. Computations on model lithiosilylenes support these assignments.

Original language	English
Pages (from-to)	426-427
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	130
Issue number	2
DOIs	https://doi.org/10.1021/ja077628v
Publication status	Published - 2008 Jan 16
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Tri-tert-butylsilylsilylenes with alkali metal substituents ( tBu3Si)SiM (M = Li, K): Electronically and sterically accessible triplet ground states",

abstract = "Lithium-, sodium-, and potassium-substituted silirenes 2a-c have been prepared by the reaction of bis(tri-tert-butylsilyl)silirene 1 with the corresponding alkali metals and characterized by NMR spectroscopy and chemical trapping (2a and 2b). Lithio- and potassiosilylenes, Li(tBu3Si)2Si: (4a) and K(tBu3Si)2Si: (4b), were generated by low-temperature irradiation of 2a and 2b, respectively, and their EPR spectra revealed the characteristic broad EPR signals at 790 mT for 4a and 780 mT for 4b. The Curie law dependence observed for 4a was in accord with a triplet ground state, also assigned to 4b. Computations on model lithiosilylenes support these assignments.",

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T1 - Tri-tert-butylsilylsilylenes with alkali metal substituents ( tBu3Si)SiM (M = Li, K)

T2 - Electronically and sterically accessible triplet ground states

AU - Sekiguchi, Akira

AU - Tanaka, Takashi

AU - Ichinohe, Masaaki

AU - Akiyama, Kimio

AU - Gaspar, Peter P.

PY - 2008/1/16

Y1 - 2008/1/16

N2 - Lithium-, sodium-, and potassium-substituted silirenes 2a-c have been prepared by the reaction of bis(tri-tert-butylsilyl)silirene 1 with the corresponding alkali metals and characterized by NMR spectroscopy and chemical trapping (2a and 2b). Lithio- and potassiosilylenes, Li(tBu3Si)2Si: (4a) and K(tBu3Si)2Si: (4b), were generated by low-temperature irradiation of 2a and 2b, respectively, and their EPR spectra revealed the characteristic broad EPR signals at 790 mT for 4a and 780 mT for 4b. The Curie law dependence observed for 4a was in accord with a triplet ground state, also assigned to 4b. Computations on model lithiosilylenes support these assignments.

AB - Lithium-, sodium-, and potassium-substituted silirenes 2a-c have been prepared by the reaction of bis(tri-tert-butylsilyl)silirene 1 with the corresponding alkali metals and characterized by NMR spectroscopy and chemical trapping (2a and 2b). Lithio- and potassiosilylenes, Li(tBu3Si)2Si: (4a) and K(tBu3Si)2Si: (4b), were generated by low-temperature irradiation of 2a and 2b, respectively, and their EPR spectra revealed the characteristic broad EPR signals at 790 mT for 4a and 780 mT for 4b. The Curie law dependence observed for 4a was in accord with a triplet ground state, also assigned to 4b. Computations on model lithiosilylenes support these assignments.

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Tri-tert-butylsilylsilylenes with alkali metal substituents ( ^tBu₃Si)SiM (M = Li, K): Electronically and sterically accessible triplet ground states

Abstract

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