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

Dalton Transactions : an International Journal of Inorganic Chemistry
Luisa López-BanetIván da Silva

Abstract

Dinuclear pentacoordinate nickel(ii) complexes of the formula [(NiTp*)2(μ-L)] (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; L = oxalate (); oxamate (); oxamidate (); OC(4-Cl-C6H4N)C(4-Cl-C6H4N)O ()) and {[Ni(N3-mc)]2(μ-L)}(PF6)2 (N3-mc = 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene; L = oxalate (); oxamate ()) have been synthesized and spectroscopically characterized (IR, (1)H NMR). X-ray structures of show nickel(ii) in a square pyramidal geometry and different supramolecular interactions. Magnetic measurements for show strong antiferromagnetic interactions across the bridging ligand [: J = -36.8 cm(-1), g = 2.16; : J = -43.6 cm(-1), g = 2.12; : J = -51.1 cm(-1), g = 2.12; : J = -39.7 cm(-1), g = 2.18; : J = -35.4 cm(-1), g = 2.20; : 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.

References

Mar 17, 2004·Inorganic Chemistry·M Dolores SantanaGregorio López
Mar 17, 2004·Angewandte Chemie·C N R RaoR Vaidhyanathan
Nov 13, 2004·Chemical Reviews·Eugenio Coronado, Peter Day
Dec 18, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·M Dolores SantanaJose Perez
Aug 10, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·A Abel LozanoMa Dolores Santana
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·M Dolores SantanaAntonio Laguna
May 25, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Rocío García-BuenoLuis García
Aug 14, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Elena A MikhalyovaAllen D Hunter

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