Issue 15, 2015

Blocking and bridging ligands direct the structure and magnetic properties of dimers of pentacoordinate nickel(ii)

Abstract

Dinuclear pentacoordinate nickel(II) complexes of the formula [(NiTp*)2(μ-L)] (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; L = oxalate (1); oxamate (2); oxamidate (3); OC(4-Cl-C6H4N)C(4-Cl-C6H4N)O (4)) and {[Ni(N3-mc)]2(μ-L)}(PF6)2 (N3-mc = 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene; L = oxalate (5); oxamate (6)) have been synthesized and spectroscopically characterized (IR, 1H NMR). X-ray structures of 1–5 show nickel(II) in a square pyramidal geometry and different supramolecular interactions. Magnetic measurements for 1–6 show strong antiferromagnetic interactions across the bridging ligand [1: J = −36.8 cm−1, g = 2.16; 2: J = −43.6 cm−1, g = 2.12; 3: J = −51.1 cm−1, g = 2.12; 4: J = −39.7 cm−1, g = 2.18; 5: J = −35.4 cm−1, g = 2.20; 6: J = −44.3 cm−1, g = 2.18]. Magneto-structural correlations between the magnitude of the magnetic coupling and the different blocking ligands, the different bridging ligands, the distortion of the coordination environment of Ni(II) and the planarity between the bridging ligand and the basal plane of the Ni(II) environment have been established for all complexes.

Graphical abstract: Blocking and bridging ligands direct the structure and magnetic properties of dimers of pentacoordinate nickel(ii)

Supplementary files

Article information

Article type
Paper
Submitted
14 Jan 2015
Accepted
24 Feb 2015
First published
02 Mar 2015

Dalton Trans., 2015,44, 6839-6847

Blocking and bridging ligands direct the structure and magnetic properties of dimers of pentacoordinate nickel(II)

L. López-Banet, M. D. Santana, G. García, J. Pérez, L. García, L. Lezama and I. da Silva, Dalton Trans., 2015, 44, 6839 DOI: 10.1039/C5DT00181A

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