Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties
- 2 March 2007
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 2007 (8) , 1091-1102
Abstract
Azido–NiII complexes of dinuclear, [Ni2(trpn)2(μ1,3‐N3)2](ClO4)2 (1), and monodimensional structures cis‐[Ni(abap)(μ1,3‐N3)]n(ClO4)n (2) and cis‐[Ni(Me6trien)(μ1,3‐N3)]n(ClO4)n·nH2O (3a) as well as the monomer [Ni(Me6trien)(N3)]ClO4 (3b) {trpn = tris(3‐aminopropyl)amine; abap = N‐(2‐aminoethyl)‐N,N‐bis(3‐aminopropyl)amine; Me6trien = 1,1,4,7,10,10‐hexamethyltriethylene tetramine} were synthesized and structurally characterized by spectroscopic techniques, X‐ray crystallography, and variable‐temperature magnetic measurements. In the complexes 1–3a, the ClO4– groups are counterions and the Ni2+ centers are bridged by the azido ligands in an end‐to‐end bonding fashion. The coordination geometry around the NiII ions is six‐coordinate with a distorted octahedral environment achieved by the four N atoms of the tetradentate amines and two terminal N atoms of the azide groups. Complex 1 consists of dinuclear units with doubly bridged azido groups whereas in 2 and 3a, a polymeric 1D chain is formed in which the adjacent azido groups link the NiII centers in a cis arrangement. In complex 2, the structural parameters of the two adjacent azido bridging ligands are different and an alternating 1D system with two different end‐to‐end azido bridges is produced. Complex 3a is a uniform 1D system where the strong steric hindrance imposed by the methyl groups of the Me6trien ligand [diagonal N(azide)–Ni–N(amine) bond angles] causes pronounced deviation from the ideal octahedral geometry. Complex 3b exhibits a distorted square pyramidal geometry. The complexes 1–3a show antiferromagnetic coupling. In complex 1, the exchange coupling constant was J = –64(1) cm–1, whereas in the polynuclear species 2 and 3a, the calculated values were J1 = –63.7(2) (α = 0.52) and J = –26.8(1) cm–1, respectively. The magnetic parameters have been correlated to the structural data.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)Keywords
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