NDLI: Binuclear nickel complexes with an edge sharing bis(square-pyramidal) $N_{3}Ni(μ-S_{2})NiN_{3}$ core: synthesis, characterization, crystal structure and magnetic properties

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kersting, Berthold Lehmann, Ulrike Loose, Claudia Lach, Jochen Hahn, Torsten Kortus, Jens
Description	Author Affiliation: Lehmann U ( Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, 04103 Leipzig, Germany.)
Abstract	The synthesis of the novel macrocyclic octadentate amino-thiophenolate ligand $H_{2}L2$ $(3,7,11,19,23,27-hexaaza-33,34-dithiol-15,31-di(tert-butyl)-tricyclo[27,3,1^{13.17}]-tetratriaconta-1(32),13,15,17(34),29,30-hexane)$ and its ability to support binuclear nickel(II) complexes with dithiolato-bridged square-pyramidal $Ni^{II}$ ions are reported. $H_{2}L2$ is obtained as the hexahydrobromide salt from a Schiff-base condensation reaction between 1,2-bis(4-tert-butyl-2,6-diformylphenylthio)ethane and bis(3-aminopropyl)amine followed by two successive reductions with $NaBH_{4}$ and $Na/NH_{3}.$ The ligand forms a green, paramagnetic, binuclear nickel(II) complex dication $[Ni^{II}_{2}L2]^{2+},$ which can be isolated as a $ClO_{4}^{−}$ (4) or $BPh_{4}^{−}$ salt (5). The binuclear nickel(II) complex contains a central $N_{3}Ni(μ-S)_{2}NiN_{3}$ core with two square-pyramidal coordinated $Ni^{II}$ ions. The $[Ni_{2}L2]^{2+}$ dication does not bind further coligands, in striking contrast to the behaviour of the parent $[Ni_{2}L1]^{2+}$ dication supported by the smaller $(L1)^{2−}$ macrocycle (containing diethylenetriamine in place of the dipropylenetriamine units) which readily binds a variety of other coligands (L′) to form bisoctahedral $[Ni_{2}L1(L′)]^{+}$ structures. The unusual behaviour of 4 relates to two different N configurations which leads to a steric shielding of the third bridging position by the $CH_{2}-groups$ of the dipropylenetriamine chains. An analysis of the temperature-dependent magnetic susceptibility data of 5 reveals the presence of a weak antiferromagnetic exchange interaction between the spins of the nickel(II) ions with a value for the magnetic exchange coupling constant J of −23.5 $cm^{−1}$ (H = $−2JS_{1}S_{2}).$ These results are further substantiated by DFT calculations.
ISSN	14779226
Issue Number	4
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-01-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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