Structure and Solution Reactivity of (Triethylsilylium)triethylsilane Cations

被引：89

作者：

Connelly, Samantha J. ^{[1
]}

Kaminsky, Werner ^{[1
]}

Heinekey, D. Michael ^{[1
]}

机构：

[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 24期

基金：

美国国家科学基金会;

关键词：

TRIETHYLSILYL CATIONS; SILYLIUM CATIONS; COORDINATION; CHEMISTRY; CRYSTAL;

D O I：

10.1021/om400970j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of triphenylmethylium tetrakis(pentafluorophenyl)borate, [Ph3C] [B(C6F5)(4)], with excess neat triethylsilane affords triethylsilylium(triethylsilane) tetrakis(pentafluorophenyl)borate, [(Et3Si)(2)(mu-H)] [B(C6F5)(4)] (1), identified by X-ray crystallography. In chlorobenzene and fluorobenzene, 1 is observed in solution. When 1 is dissolved in benzene or toluene, the evolved gas was shown to be hydrogen. Isotope labeling experiments demonstrate that the hydrogen arises from the reaction of Et3SiH with the silylium complex of the arene solvent.

引用

页码：7478 / 7481

页数：4

共 26 条

[1] Solvated silylium cations: Structure determination by NMR spectroscopy and the NMR/Ab initio/IGLO method [J].

Arshadi, M ;

Johnels, D ;

Edlund, U ;

Ottosson, CH ;

Cremer, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (21) :5120-5131

[2] Novel weak coordination to silylium ions: formation of nearly linear Si-H-Si bonds [J].

Hoffmann, SP ;

Kato, T ;

Tham, FS ;

Reed, CA .

CHEMICAL COMMUNICATIONS, 2006, (07) :767-769

[3] TRANSITION-METAL CHEMISTRY OF HEXAFLUOROBUTADIENE - FACILE HYDROLYSIS OF (HEXAFLUORO-1-METALLA-3-CYCLOPENTENE)RHODIUM COMPLEXES TO GIVE TETRAFLUORO-1-METALLA-3-CYCLOPENTEN-2-ONE AND TETRAFLUORO-1-METALLA-2-CYCLOPENTEN-4-ONE COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURES OF TRANS-[(RH-CF2CF=CF-CO)CL(PPH3)2], MER-[(RH-CF2CF=CF-CF2)CL(PME3)3], AND MER-[(RH-CF=CF-CO-CF2)CL(PME3)3] [J].

HUGHES, RP ;

ROSE, PR ;

RHEINGOLD, AL .

ORGANOMETALLICS, 1993, 12 (08) :3109-3117

[4] Silylium-Arene Adducts: An Experimental and Theoretical Study [J].

Ibad, Muhammad Farooq ;

Langer, Peter ;

Schulz, Axel ;

Villinger, Alexander .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (51) :21016-21027

[5]

Khalimon A.Y., 2007, Angew. Chem, V119, P4614

[6] Crystallographic evidence for a free silylium ion [J].

Kim, KC ;

Reed, CA ;

Elliott, DW ;

Mueller, LJ ;

Tham, F ;

Lin, LJ ;

Lambert, JB .

SCIENCE, 2002, 297 (5582) :825-827

[7] Preparation of the first tricoordinate silyl cation [J].

Lambert, JB ;

Zhao, Y ;

Zhang, SM .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2001, 14 (06) :370-379

[8] CRYSTAL-STRUCTURE OF A SILYL CATION WITH NO COORDINATION TO ANION AND DISTANT COORDINATION TO SOLVENT [J].

LAMBERT, JB ;

ZHANG, SH ;

STERN, CL ;

HUFFMAN, JC .

SCIENCE, 1993, 260 (5116) :1917-1918

[9]

LAMBERT JB, 1994, SCIENCE, V263, P984, DOI 10.1126/science.263.5149.984

[10] The trimesitylsilylium cation [J].

Lambert, JB ;

Zhao, Y .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (04) :400-401

← 1 2 3 →