Reactivity Study of Pyridyl-Substituted 1-Metalla-2,5-diaza-cyclopenta-2,4-dienes of Group 4 Metallocenes.
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 H2 , CO2 , 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 CO2 , 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 CH3 -C≡N, PhCH2 -C≡N or acetone. For CH3 -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, PhPCl2 , PhPSCl2 and SOCl2 . In the last case, the respective thiadiazole oxides and the metallocene dichlorides were obtained. A subsequent reaction produced thiadiazoles.
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Lisanne
L
Becker
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Fabian
http://orcid.org/0000-0002-1119-0343
F
Reiß
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Kai
K
Altenburger
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Anke
A
Spannenberg
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Perdita
P
Arndt
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Haijun
H
Jiao
Leibniz-Institut für Katalyse e.V. an der, Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany. uwe.rosenthal@catalysis.de.
Uwe
U
Rosenthal
exchange reaction; metallacycles; metallocenes; reactivity; small molecules