AN OPEN STRUCTURE FOR THE ADDUCT OF FLUORIDE-ION WITH OXALYL FLUORIDE

被引：6

作者：

DIXON, DA

FARNHAM, WB

SMART, BE

机构：

[1] Central Research & Development Department, E. I. du Pont de Nemours & Company, Experimental Station, Wilmington

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 20期

关键词：

D O I：

10.1021/ic00345a010

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Stable, isolable tris(dimethylamino)sulfonium salts of the perfluoroalkoxides FC(O)(CF2)nCF2O−(n = 0, 1,3) and −OCF2−(CF2)nCF2O−(n = 1, 3) have been synthesized and characterized. The C2F3O2−anion generated from oxalyl fluoride has an open ground-state structure FC(O)CF2O−and not a bridged-fluoride structure as previously proposed. High-level ab initio calculations on the isomers of C2F3O2−, including vibrational spectra calculations, corroborate the open structure. The bridged structures for C2F3O2−actually are transition states for intramolecular fluoride transfers. © 1990, American Chemical Society. All rights reserved.

引用

页码：3954 / 3960

页数：7

共 25 条

[1] INFRARED MATRIX-ISOLATION STUDY OF THE TRIHALOMETHOXY ANIONS [J].

AULT, BS .

JOURNAL OF PHYSICAL CHEMISTRY, 1980, 84 (25) :3448-3450

[2] MATRIX-ISOLATION STUDY OF THE FLUORIDE ADDUCT OF OXALYL FLUORIDE - EVIDENCE FOR A FLUORINE-BRIDGED ANION [J].

AULT, BS .

INORGANIC CHEMISTRY, 1986, 25 (07) :1013-1015

[3] VAN DER WAALS VOLUMES + RADII [J].

BONDI, A .

JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (03) :441-+

[4] STRUCTURES AND STABILITIES OF FLUORINATED CARBANIONS - EVIDENCE FOR ANIONIC HYPERCONJUGATION [J].

DIXON, DA ;

FUKUNAGA, T ;

SMART, BE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (14) :4027-4031

[5]

DIXON DA, 1987, MOL STRUCTURE ENERGE, V2, P269

[6]

DUNNING TH, 1977, METHODS ELECTRONIC S, pCH1

[7] VIBRATIONAL SPECTRA AND STRUCTURE OF OXALYL FLUORIDE IN SOLID AND FLUID STATES [J].

DURIG, JR ;

BROWN, SC ;

HANNUM, SE .

JOURNAL OF CHEMICAL PHYSICS, 1971, 54 (10) :4428-&

[8]

ENGLAND DC, 1982, Patent No. 4316986

[9] CRYSTAL AND MOLECULAR-STRUCTURE OF [(CH3)2N]3S+CF3O- - EVIDENCE FOR NEGATIVE FLUORINE HYPERCONJUGATION [J].

FARNHAM, WB ;

SMART, BE ;

MIDDLETON, WJ ;

CALABRESE, JC ;

DIXON, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (15) :4565-4567

[10] NOVEL FLUORINE-BRIDGED POLYFLUORINATED IODINE STRUCTURES - PRESENCE OF FLUORINE AS THE CENTRAL ATOM IN A 5-CENTER, 6-ELECTRON BOND [J].

FARNHAM, WB ;

DIXON, DA ;

CALABRESE, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (25) :8453-8461

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