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

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