Unusual Nitrile-Nitrile and Nitrile-Alkyne Coupling of Fc-C≡N and Fc-C≡C-C≡N

被引：37

作者：

Becker, Lisanne ^{[1
]}

Strehler, Frank ^{[2
]}

Korb, Marcus ^{[2
]}

Arndt, Perdita ^{[1
]}

Spannenberg, Anke ^{[1
]}

Baumann, Wolfgang ^{[1
]}

Lang, Heinrich ^{[2
]}

Rosenthal, Uwe ^{[1
]}

机构：

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

[2] Tech Univ Chemnitz, Fac Nat Sci, Inst Chem, D-09107 Chemnitz, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 11期

关键词：

alkynes; coupling reactions; electrochemistry; metallacycles; nitriles; 2+2+2 CYCLOADDITION; ORGANOMETALLIC CHEMISTRY; COMPLEXES; REACTIVITY; METALLACYCLES; ZIRCONOCENE; LIGAND; CARBON; METALLOCENES; POTENTIALS;

D O I：

10.1002/chem.201304478

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactions of the Group4 metallocene alkyne complexes, [Cp*M-2((2)-Me3SiC2SiMe3)] (1a: M=Ti, 1b: M=Zr, Cp*=(5)-pentamethylcyclopentadienyl), with the ferrocenyl nitriles, FcCN and FcCCCN (Fc=Fe((5)-C5H5)((5)-C5H4)), is described. In case of FcCN an unusual nitrile-nitrile CC homocoupling was observed and 1-metalla-2,5-diaza-cyclopenta-2,4-dienes (3a, b) were obtained. As the first step of the reaction with 1b, the nitrile was coordinated to give [Cp*Zr-2((2)-Me3SiC2SiMe3)(NC-Fc)] (2b). The reactions with the 3-ferrocenyl-2-propyne-nitrile FcCCCN lead to an alkyne-nitrile CC coupling of two substrates and the formation of 1-metalla-2-aza-cyclopenta-2,4-dienes (4a, b). For M=Zr, the compound is stabilized by dimerization as evidenced by single-crystal X-ray structure analysis. The electrochemical behavior of 3a, b and 4a, b was investigated, showing decomposition after oxidation, leading to different redox-active products.

引用

页码：3061 / 3068

页数：8

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