Synthesis and characterization of the non-kekule, singlet biradicaloid Ar'Ge(μ-NSiMe3)2GeAr′ (Ar′=2,6-dipp2C6H3, dipp=2,6-i-Pr2C6H3)

被引：161

作者：

Cui, CM ^{[1
]}

Brynda, M ^{[1
]}

Olmstead, MM ^{[1
]}

Power, PP ^{[1
]}

机构：

[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 21期

关键词：

D O I：

10.1021/ja0492182

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reaction of Ar′GeGeAr′ (1) with an excess of Me3SiN3 gives the non-Kekulé, biradicaloid Ar′Ge(μ-NSiMe3)2GeAr′ (3, Ar′ = 2,6-Dipp2C6H3, Dipp = 2,6-i-Pr2C6H3) which has a planar Ge2N2Si2 array and pyramidal geometry at the germaniums. DFT calculations for the model MeGe(μ-NSiH3)2GeMe indicate no Ge-Ge bonding and a singlet ground state. The calculated energy difference between the optimized singlet and triplet states is 17.51 kcal/mol. Copyright © 2004 American Chemical Society.

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页码：6510 / 6511

页数：2

相关论文

共 35 条

[1] On the electronic character of localized singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals: Substituent effects on the lifetime [J].

Abe, M ;

Adam, W ;

Hara, M ;

Hattori, M ;

Majima, T ;

Nojima, M ;

Tachibana, K ;

Tojo, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6540-6541

[2] Photochemical generation and methanol trapping of localized 1,3 and 1,4 singlet diradicals derived from a spiroepoxy-substituted cyclopentane-1,3-diyl [J].

Abe, M ;

Adam, W ;

Nau, WM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (44) :11304-11310

[3] Intramolecular and intermolecular reactivity of localized singlet diradicals: The exceedingly long-lived 2,2-diethoxy-1,3-diphenylcyclopentane-1,3-diyl [J].

Abe, M ;

Adam, W ;

Heidenfelder, T ;

Nau, WM ;

Zhang, XY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (09) :2019-2026

[4] The role of the 2,4,6-tris(trifluoromethyl)phenylamino group in stabilizing new phosphorus-, arsenic-, and germanium-containing main-group compounds and transition-metal derivatives [J].

Ahlemann, JT ;

Roesky, HW ;

Murugavel, R ;

Parisini, E ;

Noltemeyer, M ;

Schmidt, HG ;

Muller, O ;

HerbstIrmer, R ;

Markovskii, LN ;

Shermolovich, YG .

CHEMISCHE BERICHTE-RECUEIL, 1997, 130 (08) :1113-1121

[5] Radical-type reactivity of the 1,3-dibora-2,4-diphosphoniocyclobutane-1,3-diyl [J].

Amii, H ;

Vranicar, L ;

Gornitzka, H ;

Bourissou, D ;

Bertrand, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (05) :1344-1345

[6]

Baines K. M., 1996, ADV ORGANOMET CHEM, V39, P275, DOI DOI 10.1016/S0065-3055(08)60470-0

[7] Lithium phosphoranylidene carbenoids Mes*-P(=E)=C(X)Li(THF)3 (E = NMes*, C(SiMe3)2; X = Br, Cl, F):: Synthesis and structural investigations in solution and solid state [J].

Baumgartner, T ;

Gudat, D ;

Nieger, M ;

Niecke, E ;

Schiffer, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (25) :5953-5960

[8]

BORDEN WT, 1998, DIRADICALS, P708

[9]

Grützmacher H, 2002, ANGEW CHEM INT EDIT, V41, P4006, DOI 10.1002/1521-3773(20021104)41:21<4006::AID-ANIE4006>3.0.CO

[10]

2-I

← 1 2 3 4 →