Issue 4, 2012
From the journal:

Dalton Transactions

Synthesis and mononuclear complexes of the bis-bidentate ligand2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd): spin crossover in [FeII(dptd)2(NCSe)2] and [FeII(dptd)2(NCBH3)2]·H2O†

Julia Klingele,*a   Dominic Kaase,a   Marco H. Klingelea  and  Jochen Lachb  

* Corresponding authors

a Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, Freiburg, Germany
E-mail: julia.klingele@ac.uni-freiburg.de
Fax: +49-(0)761-203-6001
Tel: +49-(0)761-203-6135

b Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, Leipzig, Germany

Abstract

A simple and convenient protocol for the synthesis of the ligand 2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd) has been developed. Five new 2 : 1-type iron(II), cobalt(II), nickel(II) and copper(II) complexes have been prepared and structurally characterised, all of which feature the mononuclear trans-(N′,N1)2 coordination mode. Spin crossover behaviour has been found for [FeII(dptd)2(NCSe)2] (2) and [FeII(dptd)2(NCBH3)2]·H2O (3·H2O) with T1/2 = 192 and 285 K, respectively, reflecting the increasing ligand field strength of the respective co-ligands and showing that the [FeII(dptd)2L2] unit is suitable for the investigation of the co-ligand field effects on T1/2. In addition, the 3 : 1-type low-spin complexes [FeII(dptd)3]{B(CN)4}2·3MeOH (4·3MeOH) and [FeII(dptd)3](OTf)2·1.25DCM·0.5H2O (5·1.25DCM·0.5H2O) have been studied by X-ray diffraction and have been found to exist exclusively as the mer or fac stereoisomer, respectively, in the solid state. In MeCN-d3 solution the latter two complexes, as well as [FeII(dptd)3](ClO4)2·H2O (6·H2O), show counterion-independent stereoisomerisation, each yielding a ca. 3 : 1 mixture of mer and fac stereoisomers as identified by 1H NMR spectroscopy.

Graphical abstract: Synthesis and mononuclear complexes of the bis-bidentate ligand 2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd): spin crossover in [FeII(dptd)2(NCSe)2] and [FeII(dptd)2(NCBH3)2]·H2O

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Article information

DOI
https://doi.org/10.1039/C1DT11396H
Article type
Paper
Submitted
24 Jul 2011
Accepted
24 Oct 2011
First published
29 Nov 2011

Dalton Trans., 2012,41, 1397-1406

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Synthesis and mononuclear complexes of the bis-bidentate ligand 2,5-di(2-pyridyl)-1,3,4-thiadiazole (dptd): spin crossover in [FeII(dptd)2(NCSe)2] and [FeII(dptd)2(NCBH3)2]·H2O

J. Klingele, D. Kaase, M. H. Klingele and J. Lach, Dalton Trans., 2012, 41, 1397 DOI: 10.1039/C1DT11396H

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