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A Series of Transition Metal Bis(dicyanobenzenedithiolate) Complexes [M(dcbdt) 2 ] (M = Fe, Co, Ni, Pd, Pt, Cu, Au and Zn)
Author(s) -
Alves Helena,
Simão Dulce,
Cordeiro Santos Isabel,
Gama Vasco,
Teives Henriques Rui,
Novais Horácio,
Almeida Manuel
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300476
Subject(s) - isostructural , chemistry , triclinic crystal system , monoclinic crystal system , crystallography , electron paramagnetic resonance , square pyramidal molecular geometry , transition metal , magnetic susceptibility , ligand (biochemistry) , metal , coordination geometry , paramagnetism , tetrahedral molecular geometry , stereochemistry , crystal structure , molecule , nuclear magnetic resonance , hydrogen bond , biochemistry , physics , receptor , organic chemistry , quantum mechanics , catalysis
A series of new M[(dcbdt) 2 ] − z complexes of the dicyanobenzodithiolate (dcbdt) ligand with a range of transition metals (M = Co, Pd, Pt, Cu, Au and Zn) in different oxidation states ( z = 0.4, 1, 2) were prepared as their n Bu 4 N salts and characterised by X‐ray diffraction, cyclic voltammetry, EPR and static magnetic susceptibility. Their properties are discussed in comparison with the Ni and Fe analogues described by us recently. The structures of these complexes belong to four distinct groups: i) the Zn II compound 10 is triclinic P $\bar 1$ with the metal in a tetrahedral coordination geometry; ii) other M II complexes [M = Pt ( 8 ), Pd ( 7 ), Co ( 3 ) and Cu ( 5 )] are monoclinic C 2/ m , and are isostructural with the Ni II analogue, presenting a perfectly planar square geometry; iii) the Co III compound 4 is triclinic P $\bar 1$ , and isostructural with the Fe and Ni analogues, with a strong dimerisation of the M(dcbdt) 2 units and the metal in a square‐pyramidal coordination geometry; iv) the M III salts with M = Au ( 2 ), Cu ( 6 ) and Pt ( 9 ) are monoclinic P 2 1 / c and the complexes are arranged as pseudo‐dimers. The EPR and static magnetic‐susceptibility measurements show that the Co II ( 3 ), Cu II ( 5 ), Pt III ( 9 ) and Co III ( 4 ) complexes are paramagnetic corresponding to an S = 1/2 state, except for Co III , which is in a high‐spin S = 1 configuration. The solid state EPR spectra of the Co II compound presents a hyperfine structure typical of the I = 7/2 59 Co. The temperature dependence of the paramagnetic susceptibility of the Pt III compound follows a singlet‐triplet model with a dimer antiferromagnetic coupling, J , of 984 K. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)