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Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes
Author(s) -
Becker Lisanne,
Reiß Fabian,
Altenburger Kai,
Spannenberg Anke,
Arndt Perdita,
Jiao Haijun,
Rosenthal Uwe
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601337
Subject(s) - reactivity (psychology) , chemistry , acetonitrile , metallocene , medicinal chemistry , nitrile , molecule , thiadiazoles , diene , acetone , metallacycle , stereochemistry , organic chemistry , x ray crystallography , polymerization , medicine , natural rubber , alternative medicine , pathology , polymer , physics , diffraction , optics
In this work the reactivity of 1‐metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of group 4 metallocenes, especially of the pyridyl‐substituted examples, towards small molecules is investigated. The addition of H 2 , CO 2 , Ph−C≡N, 2‐py−C≡N, 1,3‐dicyanobenzene or 2,6‐dicyanopyridine results in exchange reactions, which are accompanied by the elimination of a nitrile. For CO 2 , a coordination to the five‐membered cycle occurs in case of Cp* 2 Zr(N=C(2‐py)−C(2‐py)=N). A 1,4‐diaza‐buta‐1,3‐diene complex is formed by H‐transfer in the conversion of the analogous titanocene compound with CH 3 −C≡N, PhCH 2 −C≡N or acetone. For CH 3 −C≡N a coupling product of three acetonitrile molecules is established additionally. In order to split off the metallocene from the coupled nitriles, we examined reactions with HCl, PhPCl 2 , PhPSCl 2 and SOCl 2 . In the last case, the respective thiadiazole oxides and the metallocene dichlorides were obtained. A subsequent reaction produced thiadiazoles.