Solvent-dependent circular dichroism of trans-disubstituted Bis(R-propane-1,2-diamine)cobalt(III) complexes

Hawkins C.J., Lawrance G.A. and Peachey R.M. (1977) Solvent-dependent circular dichroism of trans-disubstituted Bis(R-propane-1,2-diamine)cobalt(III) complexes. Australian Journal of Chemistry, 30 10: 2115-2132. doi:10.1071/CH9772115


Author Hawkins C.J.
Lawrance G.A.
Peachey R.M.
Title Solvent-dependent circular dichroism of trans-disubstituted Bis(R-propane-1,2-diamine)cobalt(III) complexes
Journal name Australian Journal of Chemistry   Check publisher's open access policy
ISSN 1445-0038
Publication date 1977-01-01
Sub-type Article (original research)
DOI 10.1071/CH9772115
Volume 30
Issue 10
Start page 2115
End page 2132
Total pages 18
Subject 1600 Chemistry
Abstract The circular dichroism spectra of trans-disubstituted bis(R-propane-1,2-diamine)cobalt(III) complexes are reported for an extended series of solvents. The observed variations in the spectra of the dichloro and dibromo complexes are analysed in terms of stereoselective solvation at the diamine N-H protons, and also the ion association between the complexes and their counter-ions. The solvation of these dihalo complexes, which was studied by p.m.r., showed a preference for hydrogen-bond formation with the equatorial N-H protons, rendering the donor nitrogens asymmetric and thus introducing a new source of dissymmetry close to the metal ion chromophore. This affected a decrease in the positive rotational strength of the 1A1g {equivalent to} 1Eg (D4h) transition, and a positive contribution to the rotational strength of the 1A1g {equivalent to} 1A2g (D4h) component. Ion association of the dihalo complexes was evaluated by a comparison of the circular dichroism of the tetraphenylborate and halide salts. The tendency for ion association was much greater for the tripositive diammine complex. However, stereospecific solvation was of little importance and the circular dichroism spectra did not show any marked solvent dependence for the tetraphenylborate salt.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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