Two oxidation states and four different coordinations of iron in an unusual chloro complex TG-MS, Raman and Mossbauer spectroscopic investigations ofthe thermal behaviour

Conventional simultaneous thermal analysis, capillary-coupled TG-MS, in sit u and ex situ Raman and Mossbauer spectroscopy, as well as chemical analysi s have been used for the investigation of the first decomposition step of t he mixed valence chloroferrate (dmpipzH(2))(6)[Fe(II)Cl-4](2)[Fe(III)Cl-4]( 2)[Fe(III)Cl-6]. Under argon at ca. 200 degrees C, an almost complete reduc tion proceeds in a solid state reaction forming Fe(II). It is accompanied b y the release of HCl and, to a minor degree, carbon containing species. A m ulti-phase product with at least two chloroferrate species, coke, and C,H,N -containing polymers is formed. Binuclear iron complexes, such as (dmpipzH) (2)[Fe(II)(2)Cl-6], and small amounts of (dmpipzH)[Fe(III)Cl-4] have been p roposed to be the major and minor component of the product mixture, respect ively. (C) 2000 Elsevier Science B.V. All rights reserved.