Dithiolate complexes structure

Mansour, M.A., Lachicotte, R.J., Gysling, H.J. and Eisenberg, R. (1998) Syntheses, molecular structures, and spectroscopy of gold(III) dithiolate complexes. Inorganic Chemistry, 37, 4625. 

Four-coordinate, planar iron(II)-dithiolate complexes also exhibit intermediate spin. The first example described was the tetraphenylarsonium salt of the square-planar bis(benzene-l,2-dithiolate)iron(II) dianion, (AsPh4)2[Fe(II)bdt2], which showed 5 = 0.44 mm s and AEq = 1.16 mm s at 4.2 K [157]. The electronic structure of a different salt was explored in depth by DFT calculations, magnetic susceptibility, MCD measurements, far-infra red spectroscopy and applied-field Mossbauer spectroscopy [158]. 

Le Narvor N, Robertson N, Weyland T, Kilbum JD, Underhill AE, Webster M, Svenstrup N, Becher J (1996) Synthesis, structure and properties of nickel complexes of 4,5-tetrathia-fulvalene dithiolates high conductivity in neutral dithiolate complexes. Chem Commun 1363-1364... 

The complex [perylene]2[Ni(mnt)2] showed the largest electrical conductivity among the nickel dithiolate complexes (a = 50 Q-1 cm-1 at room temperature on single crystals) but it has not yet been structurally characterized.2218,3219... 

The significant changes imposed on the dithioaromatic ligands and complexes upon sulfur addition are illustrated in the structure of the Ni(p-/-PrPhDtaXp-(-PrPhDtaS) complex (Fig. 48) (Table XXII), determined by Fackler et al. (233, 257). The same workers explored the sulfur addition and abstraction reaction in depth (232) (see also Section IV). The rates and mechanisms of substitution reactions of square planar nickel(II) 1,1 -dithiolate complexes (502) is discussed in Section IV. 

X-ray results are available for numerous tris chelate complexes, however, we will be primarily concerned with the three classes mentioned above. The most striking feature of the structural results is the adherence to D3 symmetry even in complexes which are severely distorted from the octahedral or trigonal antiprismatic D3(jn) limit. Muetterties and Guggenberger75) have recently pointed out that with the exception of about six tris(dithiolate) complexes, 18, that are close to the D3h (trigonal prismatic) limit, all structurally established tris chelates have D3 or near... 

Despite the ambiguity regarding the assignment of formal oxidation states to metal and ligand in many dithiolate complexes, the structure and properties of the benzyltriphenylphosphonium salt of tris(l,l-dicarboethoxyethylene-2,2-dithiolato)ferrate [BzPh3P]2[Fe(DED)3] (DED = structure 139) are considered486 to be best described in terms of an Fe,v complex. The structure is close in important details to that of the dithiocarbamate complex described above.485... 

The reaction of toluene-3,4-dithiol(3,4-dimercaptotoluene) and antimony trichloride in acetone yields a yellow solid Sb2(tdt)3, where tdt is the toluene-3,4-dithiolate anionic ligand (51). With the disodium salt of maleonitriledithiol ((Z)-dimercapto-2-butenedinitrile), antimony trichloride gives the complex ion [Sb(mnt)2]- , where mnt is the maleonitriledithiolate anionic ligand. This complex has been isolated as a yellow, crystalline, tetraethyl ammonium salt. The structures of these antimony dithiolate complexes have apparendy not been unambiguously determined. 

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