In:
Chemistry – A European Journal, Wiley, Vol. 22, No. 31 ( 2016-07-25), p. 10826-10838
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201601337
Language:
English
Publisher:
Wiley
Publication Date:
2016
detail.hit.zdb_id:
1478547-X
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