INSERTION OF ALKYNES INTO ZIRCONIUM NITROGEN BONDS LEADING TO 2,3-DIAZAMETALLACYCLOPENTENES - GENERATION AND REACTIVITY OF CP2ZR(N2PH2)

被引：47

作者：

WALSH, PJ ^{[1
]}

HOLLANDER, FJ ^{[1
]}

BERGMAN, RG ^{[1
]}

机构：

[1] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1992年 / 428卷 / 1-2期

基金：

美国国家卫生研究院;

关键词：

D O I：

10.1016/0022-328X(92)83217-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Methyl eta-2-1,2-diphenylhydrazido(1-)zirconocene (1) has been synthesized from the monopotassium salt of 1,2-diphenylhydrazine and Cp2Zr(Me)(CI). Heating 1 in THF causes extrusion of methane, generating the transient hydrazido complex Cp2Zr(N2Ph2) (2) which is trapped by solvent to yield the THF adduct Cp2Zr(N2Ph2)(THF) (3). The THF ligand of compound 3 was replaced with a variety of sigma-donor ligands to form the ligated hydrazido complexes Cp2Zr(N2Ph2)(L) (L = pyridine) (4), PMe3 (5), NCPh (6) and CNCMe3 (7)). Compound 4 was characterized by X-ray diffraction. The THF adduct 3 also undergoes a reaction involving insertion of alkynes into one of its metal-nitrogen bonds. Thus, reaction of 3 with 2-butyne and 3-hexyne leads to zirconocene 2,3-diazametallacyclopentenes 8 and 9 respectively. The structure of these metallacycles was supported by an X-ray diffraction study of 8. Compound 3 also reacted with phenylacetylene and acetophenone via deprotonation to furnish the eta-2-hydrazido(1-)acetylide (10) and enolate (11), respectively.

引用

页码：13 / 47

页数：35

共 89 条

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