CRYSTAL-STRUCTURE OF A SILYL CATION WITH NO COORDINATION TO ANION AND DISTANT COORDINATION TO SOLVENT

被引：297

作者：

LAMBERT, JB ^{[1
]}

ZHANG, SH ^{[1
]}

STERN, CL ^{[1
]}

HUFFMAN, JC ^{[1
]}

机构：

[1] INDIANA UNIV,DEPT CHEM,BLOOMINGTON,IN 47405

来源：

SCIENCE | 1993年 / 260卷 / 5116期

关键词：

D O I：

10.1126/science.260.5116.1917

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The crystal structure of a stable silyl cation, triethylsilylium, in the form of its tetrakis(pentafluorophenyl)borate salt [Et3Si+ (C6F5)4B-] (Et, ethyl) shows no coordination between cation and anion. The closest silicon-fluorine distance is greater than 4 angstroms. A toluene solvent molecule is close enough to cause some deviations from planarity at the silicon, but the silicon-toluene distance is well beyond the sum of the silicon and carbon covalent radii. The toluene molecule is essentially planar and undistorted, as expected if little or no positive charge has been transferred from silicon to toluene.

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页码：1917 / 1918

页数：2

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共 28 条

[11] CHEMISTRY OF ORGANOSILICON COMPOUNDS .292. AN NMR-STUDY OF THE FORMATION OF SILYLOXONIUM IONS BY USING TETRAKIS[3,5-BIS(TRIFLUOROMETHYL)PHENYL]BORATE AS COUNTERANION [J].

KIRA, M ;

HINO, T ;

SAKURAI, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (17) :6697-6700

[12] THE 1ST SILYLENIUM IONS IN SOLUTION [J].

LAMBERT, JB ;

SCHULZ, WJ ;

MCCONNELL, JA ;

SCHILF, W .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (07) :2201-2210

[13] TETRAKIS(PENTAFLUOROPHENYL)BORATE - A NEW ANION FOR SILYLIUM CATIONS IN THE CONDENSED PHASE [J].

LAMBERT, JB ;

ZHANG, SH .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (04) :383-384

[14] TRIMETHYLSILYL AND RELATED CATIONS IN SOLUTION [J].

LAMBERT, JB ;

KANIA, L ;

SCHILF, W ;

MCCONNELL, JA .

ORGANOMETALLICS, 1991, 10 (08) :2578-2584

[15] DO R3SI+ IONS EXIST IN SOLUTION [J].

LICKISS, PD .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (08) :1333-1338

[16] KINETICS OF HYDRIDE TRANSFER-REACTIONS FROM HYDROSILANES TO CARBENIUM IONS - SUBSTITUENT EFFECTS IN SILICENIUM IONS [J].

MAYR, H ;

BASSO, N ;

HAGEN, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (08) :3060-3066

[17] PHOTOIONIZATION MASS-SPECTROMETRY OF FLUOROMETHYLSILANES (CH3)NF4-NSI(N=1-4) [J].

MURPHY, MK ;

BEAUCHAMP, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (07) :2085-2089

[18] ORGANOMETALLIC CHEMISTRY .23. THE COVALENT NATURE OF TRIMETHYLSILYL PERCHLORATE AND OBSERVATION OF POLARIZED FLUOROTRIMETHYLSILANE-ANTIMONY PENTAFLUORIDE COMPLEXES BASED ON SI-29 NMR-STUDIES - DIFFICULTIES IN OBSERVING LONG-LIVED PERSISTENT TRIALKYLSILICENIUM IONS [J].

OLAH, GA ;

HEILIGER, L ;

LI, XY ;

PRAKASH, GKS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (16) :5991-5995

[19] THERMOCHEMISTRY OF GROUP-4A ISOBUTENE ANALOGS BY PULSED ION-CYCLOTRON DOUBLE-RESONANCE SPECTROSCOPY [J].

PIETRO, WJ ;

HEHRE, WJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (16) :4329-4332

[20] ORGANOMETALLIC CHEMISTRY .22. TRIPHENYLSILYL PERCHLORATE REVISITED - SI-29 AND CL-35 NMR-SPECTROSCOPY AND X-RAY CRYSTALLOGRAPHY SHOWING COVALENT NATURE IN BOTH SOLUTION AND THE SOLID-STATE - DIFFICULTIES IN OBSERVING LONG-LIVED SILYL CATIONS IN THE CONDENSED STATE [J].

PRAKASH, GKS ;

KEYANIYAN, S ;

ANISZFELD, R ;

HEILIGER, L ;

OLAH, GA ;

STEVENS, RC ;

CHOI, HK ;

BAU, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (17) :5123-5126