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

被引：27

作者：

Sekiguchi, Akira ^{[1
]}

Tanaka, Takashi ^{[1
]}

Ichinohe, Masaaki ^{[1
]}

Akiyama, Kimio ^{[2
]}

Gaspar, Peter P. ^{[3
]}

机构：

[1] Univ Tsukuba, Grad Sch Pure & Appl Sci, Dept Chem, Tsukuba, Ibaraki 3058571, Japan

[2] Tohoku Univ, Inst Multidisciplinary Res Adv Mat, Sendai, Miyagi 9808577, Japan

[3] Washington Univ, Dept Chem, St Louis, MO 63130 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 02期

关键词：

D O I：

10.1021/ja077628v

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Lithium-, sodium-, and potassium-substituted silirenas 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 potassiositylenes Li ((Bu3Si)-Bu-t)(2)si (4a) and K((Bu3Si)-Bu-t)(2)Si (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 lithiositylenes support these assignments.

引用

页码：426 / +

页数：3

共 14 条

[1] THE 1ST SPECTROSCOPIC DETECTION OF SILAYLIDES IN THE REACTION OF DIMESITYLSILYLENE WITH P, S, AND N HETEROATOM-CONTAINING SUBSTRATES - THE STABILITY OF SILAYLIDES [J].

ANDO, W ;

SEKIGUCHI, A ;

HAGIWARA, K ;

SAKAKIBARA, A ;

YOSHIDA, H .

ORGANOMETALLICS, 1988, 7 (02) :558-559

[2]

APELOIG Y, 1989, CHEM ORGANIC SILICON, pCH2

[3] WHEN MIGHT SILYLENES BEHAVE MORE LIKE CARBENES - SIHLI, A TRIPLET SILYLENE [J].

COLVIN, ME ;

BREULET, J ;

SCHAEFER, HF .

TETRAHEDRON, 1985, 41 (08) :1429-1434

[4]

Gaspar P P., 1998, The Chemistry of Organic Silicon Compounds, V2

[5] The quest for triplet ground state silylenes [J].

Gaspar, PP ;

Xiao, MC ;

Pae, DH ;

Berger, DJ ;

Haile, T ;

Chen, TQ ;

Lei, DQ ;

Winchester, WR ;

Jiang, P .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 646 (1-2) :68-79

[6] SPECTROSCOPIC OBSERVATION OF SILYLENE ETHER COMPLEXES [J].

GILLETTE, GR ;

NOREN, GH ;

WEST, R .

ORGANOMETALLICS, 1987, 6 (12) :2617-2618

[7] IN SEARCH OF TRIPLET SILYLENES [J].

GREV, RS ;

SCHAEFER, HF ;

GASPAR, PP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (15) :5638-5643

[8] MULTIPLICITY OF SUBSTITUTED ACYCLIC CARBENES AND RELATED MOLECULES [J].

HARRISON, JF ;

LIEDTKE, RC ;

LIEBMAN, JF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (24) :7162-7168

[9] Theory predicts triplet ground-state organic silylenes [J].

Holthausen, MC ;

Koch, W ;

Apeloig, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (11) :2623-2624

[10]

JESPERSEN KK, 1985, J AM CHEM SOC, V107, P537

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