
TY  - JOUR
A1  - Finney, AJ 
A1  - Hitchman, MA 
A1  - Raston, CL 
A1  - Rowbottom, GL 
A1  - White, AH 
T1  - Structural and spectroscopic studies of transition metal nitrite complexes. III. Crystal structures and spectra of Aquabis(<I>meso</I>-1,2-diphenylethane-1,2-diamine)-nitronickel(II) perchlorate and Bis(<I>meso</I>-1,2-diphenylethane-1,2-diamine)-(nitrito-O,O')nickel(II) chloride
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1981
VL  - 34
IS  - 10
SP  - 2069
EP  - 2084
KW  - 
UR  - https://doi.org/10.1071/CH9812069 
N2  - The crystal and molecular structures of the complexes [Ni(mstien),(NO2)(H2O)] ClO4 and [Ni(mstien)2(O2N)] Cl are reported (mstien = meso-stilbenediamine, 1,2-diphenylethane-1,2-di-amine). Both compounds contain nickel(II) in an essentially octahedral ligand environment. In the latter complex, the nitrite ion chelates, while in the former it is present as a nitro group situated trans to a coordinated water molecule. In both complexes the conformations observed for the amine chelate rings can be rationalized on the basis that they minimize intramolecular ligand repulsions. The complex [Ni(mstien)2(O2N)] NO2 is isomorphous with the analogous chloride compound, and spectral evidence suggests that the complex [Ni(mstien)2(O2N)] ClO4 also contains a chelating nitrite group. The electronic spectra of single crystals of [Ni(mstien),(O2N)] X (X = Cl- and NO2-) show bands centred at c. 25000 cm-l which exhibit vibrational fine structure. The energies of the progressional spacings are c.600cm-l, which suggests that the bands are probably due to n &#8594; &#960;* internal nitrite transitions. The band centred at c. 20500 cm-1 in [Ni(mstien)2(NO2)(H2O)] ClO4 also shows well resolved vibrational fine structure with a progressional spacing of c. 630 cm-1. This implies that the band is not due to a 'd-d' transition, but must be caused by the excitation of an electron into the nitrite &#960;* orbital, either from a non-bonding nitrite orbital, or more probably from the nickel ion. 
ER  -

