X-Ray structure, absolute configuration, and circular dichroism spectra of cobalt and chromium malonate complexes as their diastereoisomers, Δ[Co{(–)1,2-diaminopropane}3]Λ[M(malonate)3],3H2O

1976 ◽  
pp. 251-258 ◽  
Author(s):  
Keith R. Butler ◽  
Michael R. Snow
Keyword(s):  
Circular Dichroism ◽  
Absolute Configuration ◽  
Circular Dichroism Spectra ◽  
X Ray ◽  
Circular Dichroïsm

Stereospecific induction

1967 ◽  
Vol 297 (1448) ◽  
pp. 88-95 ◽  
Keyword(s):  
Circular Dichroism ◽  
Transition Metal ◽  
Absolute Configuration ◽  
Rotatory Dispersion ◽  
Central Metal ◽  
Circular Dichroism Spectra ◽  
Crystal Field Theory ◽  
X Ray ◽  
The Absolute ◽  
Circular Dichroïsm

The first resolution of an inorganic transition metal complex by Werner (1911), over fifty years ago, made possible the study of the optical activity of the metal chromophore. In his classic studies, Werner (1912 a ) resolved the cis -bis-ethylene-diamine and tris-ethylenediamine systems of tervalent cobalt. Since the absolute configuration of no dissymmetric complex was known, early studies were devoted mainly to correlating the configurations of structurally related complexes with one another. A number of rules were proposed for this purpose, the most notable of which (Werner 1912 b ) asserted that when a common resolving reagent was employed, similar complexes forming the less soluble diasterioisomers had the same absolute configuration. In addition, it was tacitly assumed that structurally similar complexes of the same central metal would give similar rotatory dispersion and circular dichroism spectra. Thus, the bis -ethylenediamine (en) complexes of cobalt (III) of the type cis -[Co en 2 X 2 ] n + were shown (Mathieu 1936) to have rotatory dispersion and circular dichroism spectra, which in most cases were consistent with the diasteriomeric solubility criterion. It was only with the re-emergence of the crystal field theory (Bethe 1929), the determination of the absolute configuration of the tris-ethylenediamine cobalt (III) ion [Co en 3 ] 3+ by X-ray diffraction (Saito, Nakatsu, Shiro & Kuroya 1957), and the use (Corey & Bailar 1959) of optically active bidentate ligands of known absolute configuration that the transition metal chromophore had a reasonable spectroscopic base and in the case of tris-bidentate systems an absolute stereo­-chemical reference point. As yet, no absolute configuration of a bis -bidentate system has been determined by the X-ray method, and there seems no simple chemical method by which the tris- and bis-bidentate complexes can be related; although recently (McCaffery, Mason & Norman 1965) a spectroscopically based relation has been put forward.

Absolute configuration of eremophilane sesquiterpenes fromPetasites hybridus: Comparison of experimental and calculated circular dichroism spectra

Chirality ◽  
2009 ◽  
pp. NA-NA ◽  
Author(s):  
Antje Bodensieck ◽  
Walter M.F. Fabian ◽  
Olaf Kunert ◽  
Ferdinand Belaj ◽  
Sajid Jahangir ◽  
...  
Keyword(s):  
Circular Dichroism ◽  
Absolute Configuration ◽  
Circular Dichroism Spectra ◽  
Circular Dichroïsm

Absolute configuration determination of theanti-head-to-head photocyclodimer of anthracene-2-carboxylic acid through cocrystallization withL-prolinol

2013 ◽  
Vol 69 (11) ◽  
pp. 1411-1413 ◽  
Author(s):  
Yuko Kawanami ◽  
Hidekazu Tanaka ◽  
Jun-ichi Mizoguchi ◽  
Nobuko Kanehisa ◽  
Gaku Fukuhara ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Circular Dichroism ◽  
Carboxylic Acid ◽  
Absolute Configuration ◽  
Void Space ◽  
Circular Dichroism Spectra ◽  
The Absolute ◽  
Circular Dichroïsm ◽  
Hydrogen Bonded

The absolute configuration has been established of the enantiopureanti-head-to-head cyclodimer of anthracene-2-carboxylic acid (AC) cocrystallized with L-propinol and dichloromethane [systematic name: (S)-2-(hydroxymethyl)pyrrolidin-1-ium (5R,6S,11R,12S)-8-carboxy-5,6,11,12-tetrahydro-5,12:6,11-bis([1,2]benzeno)dibenzo[a,e][8]annulene-2-carboxylate dichloromethane monosolvate], C5H12NO+·C30H19O4−·CH2Cl2. In the crystal structure, the AC dimer interacts with L-prolinol through a nine-membered hydrogen-bonded ring [R22(9)], while the dichloromethane molecule is incorporated to fill the void space. The absolute configuration determined in this study verifies a recent assignment made by comparing theoreticalversusexperimental circular dichroism spectra.

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