Protolysis of Seven-Membered Zirconacyclocumulene Complexes of Zirconocene

被引：6

作者：

Burlakov, Vladimir V. ^{[1
]}

Andreev, Maxim, V ^{[1
]}

Bogdanov, Vyacheslav S. ^{[1
]}

Arndt, Perdita ^{[2
]}

Baumann, Wolfgang ^{[2
]}

Spannenberg, Anke ^{[2
]}

Rosenthal, Uwe ^{[2
]}

Shur, Vladimir B. ^{[1
]}

机构：

[1] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia

[2] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany

来源：

ORGANOMETALLICS | 2020年 / 39卷 / 13期

关键词：

CHEMISTRY;

D O I：

10.1021/acs.organomet.0c00182

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The interaction of the seven-membered zirconacyclocumulene complex Cp2Zr[?4-Me(3)SiC4(SiMe3)C(C2SiMe3)=CSiMe3] (1) with an equimolar amount of HCl in dioxane at 20 degrees C results in the formation of the complex Cp2Zr(Cl)C(C=CSiMe3)-C(SiMe3)C(C=CSiMe3)=CH(SiMe3) (4), wherein one of the C=C groups is coordinated with the Zr atom. Under similar conditions, the reaction of 1 with an excess of HCl affords Cp2ZrCl2 and a mixture cis,cis- and cis,trans-unsaturated compounds H(Me3Si)C-C(C2SiMe3)C(SiMe3)-CH(C2SiMe3) (5) and H(Me3Si)C-C(C2SiMe3)C(SiMe3)-C(H)C2SiMe3 (6). The isomeric seven-membered zirconacyclocumulene Cp2Zr[?4-Me(3)SiC4(SiMe3)C(SiMe3)-C(C2SiMe3)] (2) reacts with 2 equiv of HCl in dioxane to give Cp2ZrCl2, H(Me3SiC2)C-C(SiMe3)C(SiMe3)-C(C2SiMe3)H (7), and H(Me3SiC2)C-C(SiMe3)C(SiMe3)-C-C-C(SiMe3)H (8). The subsequent reaction of this mixture with Mg in THF yields zirconabicycles 9 and 10, respectively, containing fused zirconacyclopentadiene and cyclohexadiene rings, and, correspondingly, zirconacyclopentene and cyclopentadiene cycles. From the interaction of 7 with Cp*2ZrCl2 and Mg in THF, complex 11, analogous to 9, was isolated. The protolysis of the seven-membered zirconacyclocumulene Cp2Zr[?4-PhC4(Ph)(o-C6H4)] (3) with 2 equiv of HCl yields Cp2ZrCl2 and Ph2C-C(H)C=CPh (16). The structures of 4, 7, 10, and 11 have been established by X-ray crystallography. The mechanisms of the reactions found are discussed.

引用

页码：2365 / 2374

页数：10

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