Universität zu Köln

Schueren, Andreas O., Ridgway, Benjamin M., Di Salvo, Florencia, Carella, Luca M., Gramm, Verena K., Metzger, Elisa, Doctorovich, Fabio, Rentschler, Eva ORCID: 0000-0003-1431-3641, Schuenemann, Volker, Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 and Klein, Axel (2023). Structural insight into halide-coordinated [Fe4S4XnY4-n](2-) clusters (X, Y = Cl, Br, I) by XRD and Mossbauer spectroscopy. Dalton Trans., 52 (5). S. 1277 - 1291. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

Iron sulphur halide clusters [Fe4S4Br4](2-) and [Fe4S4X2Y2](2-) (X, Y = Cl, Br, I) were obtained in excellent yields (77 to 78%) and purity from [Fe(CO)(5)], elemental sulphur, I-2 and benzyltrimethylammonium (BTMA(+)) iodide, bromide and chloride. Single crystals of (BTMA)(2)[Fe4S4Br4] (1), (BTMA)(2)[Fe4S4Br2Cl2] (2), (BTMA)(2)[Fe4S4Cl2I2] (3), and (BTMA)(2)[Fe4S4Br2I2] (4) were isostructural to the previously reported (BTMA)(2)[Fe4S4I4] (5) (monoclinic, Cc). Instead of the chloride cubane cluster [Fe4S4Cl4](2-), we found the prismane-shaped cluster (BTMA)(3)[Fe6S6Cl6] (6) (P1). Fe-57 Mossbauer spectroscopy indicates complete delocalisation with Fe2.5+ oxidation states for all iron atoms. Magnetic measurements showed small chi T-M values at 298 K ranging from 1.12 to 1.54 cm(3) K mol(-1), indicating the dominant antiferromagnetic exchange interactions. With decreasing temperature, the chi T-M values decreased to reach a plateau at around 100 K. From about 20 K, the values drop significantly. Fitting the data in the Heisenberg-Dirac-van Vleck (HDvV) as well as the Heisenberg Double Exchange (HDE) formalism confirmed the delocalisation and antiferromagnetic coupling assumed from Mossbauer spectroscopy.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Schueren, Andreas O. UNSPECIFIED UNSPECIFIED UNSPECIFIED Ridgway, Benjamin M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Di Salvo, Florencia UNSPECIFIED UNSPECIFIED UNSPECIFIED Carella, Luca M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Gramm, Verena K. UNSPECIFIED UNSPECIFIED UNSPECIFIED Metzger, Elisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Doctorovich, Fabio UNSPECIFIED UNSPECIFIED UNSPECIFIED Rentschler, Eva UNSPECIFIED orcid.org/0000-0003-1431-3641 UNSPECIFIED Schuenemann, Volker UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED Klein, Axel UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-679444
DOI:	10.1039/d2dt03203a
Journal or Publication Title:	Dalton Trans.
Volume:	52
Number:	5
Page Range:	S. 1277 - 1291
Date:	2023
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language IRON-SULFUR CLUSTERS; SUBSITE-DIFFERENTIATED ANALOGS; TERMINAL LIGAND CUBANES; SULFIDE-THIOLATE DIMERS; UNIVERSAL FORCE-FIELD; FE/MO-S/SE CUBANE; 2 DIFFERENT MODES; CRYSTAL-STRUCTURES; 4FE-4S CLUSTERS; ELECTRON-DELOCALIZATION Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/67944