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|Title:||Spectroscopic investigation of intermolecular interactions in dithiolate complexes of nickel|
|Citation:||Inorganic Chemistry, 27(8), 1492-1498|
|Abstract:||A spectroscopic study on maleonitriledithiolato complexes of the type R n[M(mnt) 2], where n = 1 or 2, M = Ni(II) or Ni(III), and R = (CH 3) 4N or (n-C 4H 9) 4N, is presented. On the basis of the charge potential model, with incorporation of electronegativities, the charges on the various atoms have been calculated by using the binding energies obtained from photoelectron spectroscopic experiments. These are found to compare well with those reported by Xa calculations. The binding energy, shifts of the atoms on [(n-C 4H 9) 4N] 2[Ni(mnt) 2] are observed to follow a different trend compared with that in the other three complexes. This difference in the charge distribution in the diamagnetic complex with tetrabutylammonium as the cation has been explained with the help of molecular projections. It has been inferred that there is an interaction between the cation and the complex anion in this case. EPR and Raman spectral studies on this complex at low temperatures (down to 20 K) are reported here. Two phase transitions, which also involve a slight molecular distortion, are detected at 50 and 20 K. Infrared spectra of all these complexes are compared, and this also reveals the same anomalous trend. In order to ascertain this behavior, single-crystal electronic spectra of [(CH 3) 4N] 2[Ni(mnt) 2] at various temperatures are reported. ? 1988 American Chemical Society.|
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