Universität zu Köln

Krackl, Sebastian, Alberola, Antonio, Llusar, Rosa ORCID: 0000-0002-3539-7269, Meyer, Gerd ORCID: 0000-0003-1000-9001 and Vicent, Cristian (2010). Use of a cubane-type Mo3CoS4 molecular cluster as paramagnetic unit in the synthesis of hybrid charge-transfer salts. Inorg. Chim. Acta, 363 (15). S. 4197 - 4202. LAUSANNE: ELSEVIER SCIENCE SA. ISSN 1873-3255

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Abstract

Selective substitution of the chlorine atom coordinated to cobalt in the paramagnetic Mo-3(CoCl)S-4 (dmpe)(3)Cl-3 (dmpe = 1,2-bis(dimethylphosphanyl) ethane) complex with a S = 1/2 ground state has been achieved by iodine oxidation to afford the also paramagnetic [Mo-3(CoI)S-4(dmpe)(3)Cl-3] I ([1]I) salt with a S = 1 ground state in almost quantitative yield. Replacement of chorine by iodine has no significant effect on the structural and electrochemical properties of the Mo3CoS4 system. Metathesis of the [1]I salt with the paramagnetic nickel anionic dithiolate [Ni(mnt)(2)] (mnt = maleonitrilodithiolate) affords [1](2)[Ni(mnt)(2)]. The stoichiometry evidenced by X-ray analysis reveals that reduction of the [Ni(mnt)(2)] radical to the corresponding diamagnetic closed shell [Ni(mnt)(2)](2) dianion, presumably via dismutation, has occurred during the metathesis process. The crystal structure of [1](2)[Ni(mnt)(2)] consists of [Ni(mnt) 2] 2 similar to dianions sandwiched by two cluster 1+ cations which yield {1(+)center dot[Ni(mnt)(2)](2)center dot 1(+)} subunits arranged along the crystallographic c axis. Magnetic susceptibility measurements for [1](2)[Ni(mnt)(2)] show a chi T product of 0.99 emu K/mol largely unchanged in the 10-300 K range. This behavior agrees with the presence of an S = 1 cluster 1(+) cation while the Ni(mnt)(2) moiety does not contribute to the paramagnetism of the sample. (C) 2010 Elsevier B. V. All rights reserved.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Krackl, Sebastian UNSPECIFIED UNSPECIFIED UNSPECIFIED Alberola, Antonio UNSPECIFIED UNSPECIFIED UNSPECIFIED Llusar, Rosa UNSPECIFIED orcid.org/0000-0002-3539-7269 UNSPECIFIED Meyer, Gerd UNSPECIFIED orcid.org/0000-0003-1000-9001 UNSPECIFIED Vicent, Cristian UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-490759
DOI:	10.1016/j.ica.2010.06.029
Journal or Publication Title:	Inorg. Chim. Acta
Volume:	363
Number:	15
Page Range:	S. 4197 - 4202
Date:	2010
Publisher:	ELSEVIER SCIENCE SA
Place of Publication:	LAUSANNE
ISSN:	1873-3255
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CRYSTAL-STRUCTURE; COMPLEXES; COEXISTENCE; MO3NIS4; HALIDE; BR; CL Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/49075