Synthetic conducting materials (I) partial oxidation of bis (difluoroborondiphenylglyoximato) nickel (II) with iodine

doi:10.1016/0379-6779(87)90449-8

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Title:	Synthetic conducting materials (I) partial oxidation of bis (difluoroborondiphenylglyoximato) nickel (II) with iodine
Authors:	王文竹;Wang, Wen-jwu;Chu, W. J.
Contributors:	淡江大學化學學系
Date:	1987-03-01
Issue Date:	2009-12-01
Publisher:	Elsevier
Abstract:	Bis(difluoroborondiphenylglyoximato) nickel(II), Ni(DPGB)2, has been synthesized which used a dioxime ligand entailing BF2 bridge. This complex was further oxidized by iodine to form partially oxidized crystal with metallic luster. The compound Ni(DPGB)2I3.93 has been shown by single-crystal X-ray diffraction to crystallize in monoclinic space group I2/c with eight formula unit in a cell of dimensions a=21.812(5) A ̊ and b=13.883(5) A ̊, c=23.612(6) A ̊. Full-matrix least-squares refinement gave a final value of R1=0.1178 for 1360 reflections. The crystal structure consists of slipped stacked Ni(DPGB)2 units, each eclipsed with respect to its nearst neighbors, and disordered zig-zag chains of iodine atoms extending in the c-direction. Resonance Raman studies indicate that the predominant form of the iodine present is I2·I3-. (fundamental transition ν=177 cm-1 vs and ν=108 cm-1 w). Thus, the Ni(DPGB)2 unit is formally in fractional oxidation state of +0.78(6). the partial oxidation of Ni(DPGB)2 was also evidenced by the infrared and mass spectrometry. Thermogram of this compound show a very small endothermic peak as weight change 35.36% which is due to the iodine loss. This shows the iodine is not chemically bonded on the nickel complex. After the iodine was removed, a new compound has a structure with an axial coordinated iodide was proposed. Powder electrical conductivity is 4.4×10-5 Ω-1cm-1 at 25°C. Variable-temperature studies show the conductivity to be thermally activated, with activation energy of 0.48 eV.
Relation:	Synthetic metals 19(1-3), pp.763-768
DOI:	10.1016/0379-6779(87)90449-8
Appears in Collections:	[Graduate Institute & Department of Chemistry] Journal Article

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