REACTION OF FLORIANIS METALLAOXIRANE [(CP2ZRCL)2(MU-ETA-1(O),ETA-2(C,O)-CH2O)] WITH ISONITRILES

被引：20

作者：

BENDIX, M ^{[1
]}

GREHL, M ^{[1
]}

FROHLICH, R ^{[1
]}

ERKER, G ^{[1
]}

机构：

[1] UNIV MUNSTER,INST ORGAN CHEM,CORRENSSTR 40,D-48149 MUNSTER,GERMANY

来源：

ORGANOMETALLICS | 1994年 / 13卷 / 08期

关键词：

D O I：

10.1021/om00020a058

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The (mu-formaldehyde)(Cp2ZrCl)2 complex 1 reacts with alkyl isocyanides RNC (R = -CH2SiMe3, -CMe3) with insertion into the Zr-C bond and opening of the metallaoxirane unit by cleavage of the adjacent Zr-O bond to give the ''N-inside'' (eta2-iminoacyl)zirconocene complexes 2(a,b) [(Cp2ZrCl)C(CH2OZrCp2Cl)= NR]. This insertion behavior of 1 is unusual as compared to the (eta2-formaldehyde)zirconocene dimer 4 that reacts with Me3SiCH3NC without Zr-O bond cleavage to give a four-membered metallacyclic (eta1-iminoacyl)zirconocene complex. The isonitrile insertion product 2a was characterized by X-ray diffraction. It crystallizes in the space group P1BAR with cell parameters a = 10.884(2) angstrom, b = 12.326(1) angstrom, c = 13.611(4) angstrom, alpha = 70.33(1)-degrees, beta = 72.57(2)-degrees, gamma = 86.43(1)-degrees, Z = 2, R = 0.045, R(w)2 = 0.125. The C=N bond length in 2a is 1.257(2) angstrom. The adjacent Zr-C(iminoacyl) bond is 2.198(4) angstrom.

引用

页码：3366 / 3369

页数：4

共 48 条

[1] ISOCYANIDE INSERTION REACTIONS .2. STRUCTURAL AND DYNAMICAL STEREOCHEMISTRY OF ETA-1-IMINOACYL AND ETA-2-IMINOACYL LIGANDS [J].

ADAMS, RD ;

CHODOSH, DF .

INORGANIC CHEMISTRY, 1978, 17 (01) :41-48

[2] TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .1. BOND LENGTHS IN ORGANIC-COMPOUNDS [J].

ALLEN, FH ;

KENNARD, O ;

WATSON, DG ;

BRAMMER, L ;

ORPEN, AG ;

TAYLOR, R .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (12) :S1-S19

[3] A NEW APPROACH FOR THE SYNTHESIS OF NEUTRAL AND ANIONIC ZIRCONOCENE ALDEHYDE COMPLEXES [J].

ASKHAM, FR ;

CARROLL, KM ;

ALEXANDER, SJ ;

RHEINGOLD, AL ;

HAGGERTY, BS .

ORGANOMETALLICS, 1993, 12 (12) :4810-4815

[4] EVIDENCE OF AN ALTERNATIVE MECHANISM FOR THE REDUCTIVE COUPLING OF ISONITRILES BY ELECTROPHILIC 1-SILA-3-ZIRCONACYCLOBUTANE COMPLEXES - STRUCTURAL CHARACTERIZATION OF THE BICYCLIC ENEDIAMIDO COMPLEXES CP2ZR(N(CME3)C(CH2SIME2CH2) = CN(R)), WHERE R = TERT-BUTYL AND 2,6-XYLYL [J].

BERG, FJ ;

PETERSEN, JL .

ORGANOMETALLICS, 1991, 10 (05) :1599-1607

[5] SYNTHETIC AND MECHANISTIC INVESTIGATION OF THE REARRANGEMENT OF ETA-2-IMINOACYL LIGANDS OF GROUP-4 METALS TO VINYLAMIDO GROUPS VIA A FACILE 1,2-HYDROGEN SHIFT [J].

BESHOURI, SM ;

CHEBI, DE ;

FANWICK, PE ;

ROTHWELL, IP ;

HUFFMAN, JC .

ORGANOMETALLICS, 1990, 9 (08) :2375-2385

[6] ON THE MECHANISM OF THE FISCHER-TROPSCH REACTION - THE CHAIN PROPAGATION STEP [J].

BRADY, RC ;

PETTIT, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (05) :1287-1289

[7] REACTIONS OF DIAZOMETHANE ON TRANSITION-METAL SURFACES AND THEIR RELATIONSHIP TO THE MECHANISM OF THE FISCHER-TROPSCH REACTION [J].

BRADY, RC ;

PETTIT, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (19) :6181-6182

[8] PREPARATION OF DINUCLEAR ZIRCONIUM HYDRIDE COMPLEXES CONTAINING THE FULVALENE LIGAND AND THEIR REACTIONS WITH CARBON-MONOXIDE [J].

CURTIS, CJ ;

HALTIWANGER, RC .

ORGANOMETALLICS, 1991, 10 (09) :3220-3226

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

DURFEE, LD ;

ROTHWELL, IP .

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

[10] REACTIONS OF (ETA-5-C5H5)(ETA-5-C5ME5)ZR[SI(SIME3)3]X (X = CL, ME) COMPLEXES WITH CARBON-MONOXIDE AND THE ISOCYANIDE 2,6-ME2C6H3NC - CRYSTAL-STRUCTURE OF (ETA-5-C5H5)-(ETA-5-C5ME5)ZR[ETA-2-C(N-2,6-ME2C6H3)SI(SIME3)3]CL [J].

ELSNER, FH ;

TILLEY, TD ;

RHEINGOLD, AL ;

GEIB, SJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 358 (1-3) :169-183

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