ISSN:
0018-019X
Schlagwort(e):
Chemistry
;
Organic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The preparation and the CD spectra of optically pure (+)-trans-μ-[(1R,4S,5S,6R,7R,8S)-C,5,6,C -η : C,7,8,C-η-(5,6,7,8-tetramethylidene-2-bicyclo [2.2.2]octanone)]bis(tricarbonyliron) ((+)-7) and (+)-tricarbonyl[(1S,4S,5S,6R)-C-5,6,C-η-(5,6,7,8,-tetramethylidene-2-bicyclo[2.2.2]octanone)]iron ((+)-8), and of its 3-deuterated derivatives (+)-trans-μ-[(1R,3R,4S,5S,6R,7R,8S)-C,5,6,C-η : C,7,8,C-η-5,6,7,8-tetramethylidene(3-D)-2-bicyclo[2.2.2]-(octanone)]bis(tricarbonyliron) ((+)-11) and (+)-tricarbonyl[(1S,3R,4S,5S,6R)-C-5,6,C- η-(5,6,7,8-tetramethylidene(3-D)-2-bicyclo[2.2.2]octanone)]iron ((+)-12) are reported. The chirality in (+)-7 and (+)-8 is due to the Fe(CO)3 moieties uniquely. The signs of the Cotton effects observed for (+)-7 and (+)-8 obey the octant rule (ketone n→π*CO transition). Optically pure (-)-3R-5,6,7,8-tetramethylidene(3-D)-2-bicyclo[2.2.2]octanone ((-)-10) was prepared. Its CD spectrum showed an ‘anti-octant’ behaviour for the ketone n→π*CO transition of the deuterium substituent. The CD spectra of the alcoholic derivatives (-)-trans-μ-[(1R,2R,4S, 5S,6R,7R,8S)-C,5,6,C-η : C,7,8,C- η-(5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octanol)]bis(tricarbonyliron) ((-)-2) and (-)-tricarbonyl- [(1S,2R,4S,5S,6R)- C,5,6,C- η-(5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octanol)]iron ((-)-3) and of the 3-denterated derivatives (-)-5 and (-)-6 are also reported. The CD spectra of the complexes (-)-2, (-)-3, (+)-7, and (+)-8 were solvent and temperature dependent. The ‘endo’-configuration of the Fe(CO)3 moiety in (±)-8 was established by single-crystal X-ray diffraction.
Zusätzliches Material:
8 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/hlca.19860690204
Permalink
