Circular dichroism spectra of asymmetric unidentate amine complexes of cobalt(III)

1973 ◽  
Vol 26 (11) ◽  
pp. 2401 ◽  
Author(s):  
CJ Hawkins ◽  
GA Lawrance

The preparations of pentaamminecobalt(III) complexes of a series of asymmetric unidentate amines are reported. The circular dichroism spectra for the (S)-amines show negative Cotton effects under the 1A1g → 1T1g absorption band, which are somewhat solvent dependent but independent of temperature down to -190�C. The vicinal effect from 1- cyclohexylethylamine was comparable to that from analogous aromatic compounds, but the simpler alkyl derivatives were found to impose smaller rotational strengths on the d-d transitions. The lack of measurable c.d. in the visible region for tetraammine((S)-butane-1,3- diamine)cobalt(III) is reported and discussed in the light of the other studies.

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.


1971 ◽  
Vol 24 (11) ◽  
pp. 2275 ◽  
Author(s):  
CJ Hawkins ◽  
GA Lawrance

The preparations of a series of optically active complexes with the general formula Co(NH3)5(OCOCH(X)CH3)2+ are reported for X = NH3+, OH, F, Cl, Br, C2H5, and C6H5. The circular dichroism spectra of the complexes have been measured in aqueous solution, in the presence of salts of polarizable anions, and in KBr disks. The spectra have been analysed in terms of three Cotton effects under the 1A1g → 1T1g cubic absorption band and found to be consistent with a +, -, - sign pattern for the L- isomer, corresponding to the two components of the 1A1g → 1Eg (D4h) and to the 1A1g → A2g (D4h) transition, respectively.


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.


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.


1976 ◽  
Vol 157 (3) ◽  
pp. 773-775 ◽  
Author(s):  
Y Looze ◽  
E Polastro ◽  
C Gielens ◽  
J Léonis

The circular-dichroism spectra of baker's-yeast iso-1- (methylated and unmethylated forms) and iso-2-cytochrome c species were examined between 200 and 600nm. In the visible region the yeast haemoproteins have characteristics nearly indistinguishable from those of horse heart cytochrome c. From the spectra in the u.v. region the latter appears, however, to be more helical. It is proposed that the likely element of non-helical structure in iso-1-cytochrome c is residues 62-70.


1981 ◽  
Vol 36 (6) ◽  
pp. 735-738 ◽  
Author(s):  
Harald Lehner ◽  
Corinna Krauss ◽  
Hugo Scheer

Abstract The applicability of solvent induced circular dichroism (SICD) for the conformational analysis of bile pigments has been investigated. The S-(-)-ethyl lactate induced rotational strengths for octaethylbilindion (4) and its dihydroderivative 5 are remarkably high. Related compounds, e.g. the isomeric purpurines 1 and 2 and formyltripyrrinon 3 exhibit an optical activity which is smaller by more than one order of magnitude. 1-3 are essentially free from steric strain so that a flat arrangement of the chromophore is most likely. On the other hand the closed conformations of 4 and 5 experience considerable steric repulsion of their terminal rings, so that a helical topology is energetically favoured. This distinction is reflected in the magnitude of the SICD observed and demonstrates its applicability for the conformational analysis of bile pigments.


1980 ◽  
Vol 34 (3) ◽  
pp. 360-363 ◽  
Author(s):  
Hans Peter Jensen

This paper shows what a marvelous thing it is to be able to get a complete dichroic tensor for an absorption band, how useful this information is, and what elegant tools there are available to help one out; namely, polarization, modulation spectroscopy, and group theory.


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