Circular dichroism spectra of tetraamminecobalt(III) complexes of amino alcohols

1978 ◽  
Vol 31 (11) ◽  
pp. 2399 ◽  
Author(s):  
CJ Hawkins ◽  
GA Lawrance ◽  
JA Palmer

The circular dichroism spectra are reported for tetraamminecobalt(III) complexes with the chiral amino alcohols 2-aminopropan-1-ol, 2- aminobutan-1-ol, 1-aminopropan-2-ol, 2-amino-1-phenyl-ethanol, ψ- ephedrine and ephedrine with the alcohol groups protonated (OH) and deprotonated (O-). The solvent dependence of the chemical shifts of the NH protons was investigated to determine the effects of stereoselective solvation on the circular dichroism, but, in contrast to some other related systems, the chemical shift difference between the two NH2 protons was relatively insensitive to solvent. Consistent with this, the circular dichroism spectra of the tetraphenylborate salts of the deprotonated complexes were found not to be markedly dependent on solvent. Tetraammine-{(-)-ψ-ephedrine)cobalt(III) and tetraammine{(-)- ephedrine}cobalt(III) were found to have the same signs of Cotton effects for the various d-d transitions, whereas bis{(-)-ψ- ephedrine}copper(II) and bis{(-)-ephedrine}copper(II) had opposite signs. This has been explained in terms of different conformer populations in the cobalt(III) and copper(II) systems.

1970 ◽  
Vol 23 (9) ◽  
pp. 1735 ◽  
Author(s):  
CJ Hawkins ◽  
PJ Lawson

The circular dichroism spectra of a series of optically active (α-aminocarboxylato)tetraamminecobalt(111) complexes have been measured in aqueous solution, and in the presence of salts of polarizable anions. The observed spectra in the visible region have been analysed to determine the signs of the Cotton effects of the three components of the 1A1g ↔ 1T1g cobalt(111) transition. For L-amino acids, the transition with A2g(D4h) parentage is negative, and the two transitions with Eg(D4h) parentage have opposite signs. Published circular dichroism spectra of complexes of the type [Co(en)2(L-am)]2+ were similarly interpreted in terms of a perturbed tetragonal chromophore, and it was shown that the vicinal effect of the L-amino acids imposed the same signs onto the component transitions as for the tetraammines and for a similar series of pentaamminecobalt(111) complexes.


1977 ◽  
Vol 30 (10) ◽  
pp. 2115 ◽  
Author(s):  
CJ Hawkins ◽  
GA Lawrance ◽  
RM Peachey

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 → 1Eg (D4h) transition, and a positive contribution to the rotational strength of the 1A1g → 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.


2005 ◽  
Vol 16 (19) ◽  
pp. 3188-3197 ◽  
Author(s):  
Jadwiga Frelek ◽  
Marcin Górecki ◽  
Jarosław Jaźwiński ◽  
Marek Masnyk ◽  
Patrycja Ruśkowska ◽  
...  

1990 ◽  
Vol 44 ◽  
pp. 42-49 ◽  
Author(s):  
Björn Ringdahl ◽  
A. Grand ◽  
M. S. Lehmann ◽  
D. E. Cox ◽  
S. Larsen ◽  
...  

1970 ◽  
Vol 23 (11) ◽  
pp. 2237 ◽  
Author(s):  
CJ Hawkins ◽  
CL Wong

The solution circular dichroism spectra of the 1 : 1 and 1 : 2 copper(II) complexes of a series of �-amino acids are reported for the region 12500-25000 cm-1. These spectra and spectra of the isolated 1 : 2 complexes dispersed in KBr disks have been interpreted as arising from three Cotton effects with a -,+,- sign pattern for the L configuration, except for the L-proline spectra, which were analysed in terms of a +,-,+ pattern. A tentative assignment is made for these Cotton effects, and the relative contributions of vicinal and conformational effects to the rotational strength are discussed.


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