THE DOUBLE INSERTION OF T-BUTYL ISOCYANIDE BY TRIS(TETRAMETHYLCYCLOPENTADIENYL)ALUMINUM TO FORM (ETA(1)-C(5)ME(4)H)(2)AL(C(=NTBU)-C(=NTBU)(C(5)ME(4)H))

被引：28

作者：

SHAPIRO, PJ ^{[1
]}

VIJ, A ^{[1
]}

YAP, GPA ^{[1
]}

RHEINGOLD, AL ^{[1
]}

机构：

[1] UNIV DELAWARE,DEPT CHEM,NEWARK,DE 19716

来源：

POLYHEDRON | 1995年 / 14卷 / 01期

关键词：

D O I：

10.1016/0277-5387(94)00354-H

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Tris(tetramethylcyclopentadienyl)aluminum, Cp(3)'Al (Cp' = C(5)Me(4)H), reacts with t-butyl isocyaniode to form (eta(1)-C(5)Me(4)H)(2)Al{c(=NtBu)-C(=NtBu)(C(5)Me(4)H)} which results from the double insertion of the isonitrile at a single Al-cyclopentadienyl ring position. Double isonitrile insertion occurs in preference to a single insertion such that only unreacted Cp(3)'Al and the title compound are observed when fewer than two equivalents of the isonitrile are consumed. The molecular structure of (eta(1)-C(5)Me(4)H)2Al{C(=NtBu)-C(=NtBu)(C(5)Me(4)H)} has been determined by single-crystal X-ray diffraction. The aluminum center is tetracoordinate with two eta(1)-cyclopentadienyl rings and the coupled isonitrile fragment bonding through a carbon of one iminoacyl group and a nitrogen of the other to form a four-membered azametallacycle.

引用

收藏

页码：203 / 209

页数：7

相关论文

共 31 条

[1] ISOCYANIDE INSERTION REACTIONS .1. IMPORTANCE OF ETA2-IMINOACYL LIGANDS AS INTERMEDIATES [J].

ADAMS, RD ;

CHODOSH, DF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (20) :6544-6550

[2] CHEMISTRY OF LOW-VALENT METAL ISOCYANIDE COMPLEXES .2. OXIDATIVE REACTIONS OF PENTAKIS(TERT-BUTYL ISOCYANIDE)IRON WITH ALKYL, ALLYL, BENZYL, FLUOROALKYL, AND PENTAFLUOROPHENYL HALIDES, AND WITH TRIMETHYLOXONIUM TETRAFLUOROBORATE AND DIPHENYLACETYLENE - EVIDENCE FOR ISOCYANIDE INSERTION REACTIONS, AND THE MOLECULAR-STRUCTURE OF [FE(CNBUT)3-[1-4-ETA-C(=NBUT)=C(PH)C(PH)=C(=NBUT)]]M [J].

BASSETT, JM ;

GREEN, M ;

HOWARD, JAK ;

STONE, FGA .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1980, (09) :1779-1788

[3]

CARMONA E, 1992, PERSPECTIVES COORDIN, P407

[4] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF EARLY TRANSITION-METAL ETA-2-IMINOACYL COMPLEXES CONTAINING ARYL OXIDE LIGATION [J].

CHAMBERLAIN, LR ;

DURFEE, LD ;

FANWICK, PE ;

KOBRIGER, L ;

LATESKY, SL ;

MCMULLEN, AK ;

ROTHWELL, IP ;

FOLTING, K ;

HUFFMAN, JC ;

STREIB, WE ;

WANG, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (02) :390-402

[5] INTRAMOLECULAR COUPLING OF ETA-2-IMINOACYL AND ETA-2-ACYL FUNCTIONS AT GROUP-4 AND GROUP-5 METAL CENTERS - STRUCTURE AND SPECTROSCOPIC PROPERTIES OF THE RESULTING ENAMIDOLATE AND ENEDIAMIDE COMPLEXES [J].

CHAMBERLAIN, LR ;

DURFEE, LD ;

FANWICK, PE ;

KOBRIGER, LM ;

LATESKY, SL ;

MCMULLEN, AK ;

STEFFEY, BD ;

ROTHWELL, IP ;

FOLTING, K ;

HUFFMAN, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (20) :6068-6076

[6] DIBUTYLMAGNESIUM, A CONVENIENT REAGENT FOR THE SYNTHESIS OF USEFUL ORGANIC MAGNESIUM REAGENTS MGA2 INCLUDING CYCLOPENTADIENYLS, ARYLOXIDES, AND AMIDES - PREPARATION OF ZR(C5H5)CL3. X-RAY STRUCTURE OF [MG(MU-N(SIME)3)C6H4N(SIME3)-0)(OET2)]2 [J].

DUFF, AW ;

HITCHCOCK, PB ;

LAPPERT, MF ;

TAYLOR, RG ;

SEGAL, JA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1985, 293 (03) :271-283

[7] CHEMISTRY OF ETA-2-ACYL, ETA-2-IMINOACYL, AND RELATED FUNCTIONAL-GROUPS [J].

DURFEE, LD ;

ROTHWELL, IP .

CHEMICAL REVIEWS, 1988, 88 (07) :1059-1079

[8] FACILE MAGNETIZATION OF CARBON BRONSTED ACIDS WITH ELECTROPHILIC, DONOR-FREE ALKYLMAGNESIUM COMPOUNDS [J].

EISCH, JJ ;

SANCHEZ, R .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1985, 296 (03) :C27-C31

[9]

EISCH JJ, 1982, COMPREHENSIVE ORGANO, V1, pCH6

[10] A (ETA-1-IMINOACYL)ZIRCONOCENE COMPLEX FORMED BY ALKYL ISOCYANIDE INSERTION INTO THE METAL TO CARBON BOND OF (ETA-2-FORMALDEHYDE)ZIRCONOCENE [J].

ERKER, G ;

MENA, M ;

KRUGER, C ;

NOE, R .

ORGANOMETALLICS, 1991, 10 (04) :1201-1203

← 1 2 3 4 →