852952-94-4Relevant academic research and scientific papers
A series of neutral radical CpNi(dithiolene). complexes
Fourmigue, Marc,Avarvari, Narcis
, p. 1365 - 1371 (2005)
The heteroleptic neutral radical dithiolene complexes CpNi(dsit) ., CpNi(dsit). and CpNi(dmid). (dmit = 1,3-dithiole-2-thione-4,5-dithiolate; dsit = 1,3-dithiole-2-thione-4,5- diselenolate; dmid = 1,3-dithiole-2-one-4,5-dithiolate) are obtained from the reaction of (Cp2Ni)BF4 with either (n-Bu 4N)[Ni(dmit)2] and (n-Bu4N)[Ni(dmid) 2] or PhSb(dmit) and PhSb(dsit), respectively. The three complexes reduce reversibly to the corresponding Ni(II) anions and oxidize reversibly to the cationic state. As deduced from DFT calculations performed on CpNi(dmit)., the SOMO of these complexes is essentially localized on the dithiolene moiety with little metal contribution. CpNi(dsit). is isostructural with CpNi(dmit). and crystallizes in the monoclinic system, space group P21. In the solid-state structures of both CpNi(dmit). and CpNi(dsit)., molecules interact through a three-dimensional set of intermolecular interactions mediated by short S ... S, Se ... Se and S ... Se contacts, as confirmed from the temperature and field dependence of the magnetic susceptibility by the observation of an antiferromagnetic ground state below TNeel = 27 K in CpNi(dmit)., 18 K in CpNi(dsit).. Finally, CpNi(dmid). crystallizes in the orthorhombic system, space group Pnma. Molecules organize into uniform chains through the stacking of the dmid moieties in a σ-type face-to-face overlap. The Royal Society of Chemistry 2005.
