ISSN:
0044-2313
Keywords:
Tetraiododicarbonylosmate(II)
;
Crystal Structure
;
Vibrational Spectra
;
Normal Coordinate Analysis
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans-(TEA)2[OsI4(CO)2]The X-ray structure determination of trans-(TEA)2[Os(CO)2I4] (monoclinic, space group P21/n, a = 10.609(2), b = 10.659(3), c = 13.229(6) Å, β = 90.46(3)°, Z = 2) revealed the rough D4th point symmetry of the complex anion trans-[Os(CO)2I4]2- (Os—I = 2.726(1), 2.727(1); Os—C = 1.91(2); C—O = 1.14(2) Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(CO) = 15.86, fd(OsC) = 3.28, fd(OsI) = 1.13 mdyn/Å. The strengthening of the Os—C bond by stronger back donation of the OsII(d6) complex in comparison with the isostructural OsIII(d5) compound is discussed.
Notes:
Die Röntgenstrukturanalyse von trans-(TEA)2[Os(CO)2I4] (monoklin, Raumgruppe P21/n, a = 10,609(2), b = 10,659(3), c = 13,229(6) Å, β = 90,46(3)°, Z = 2) hat gezeigt, daß das centrosymmetrische Komplexanion trans-[Os(CO)2I4]2- (Os-I = 2,726(1), 2,727(1); Os-C = 1,91(2); C—O = 1,14(2) Å) annähernd D4th-Punktsymmetrie aufweist. Mit den röntgenographisch bestimmten Molekülparametern lassen sich die IR- und Raman-Spektren durch Normalkoordinatenanalyse zuordnen. Die Valenzkraftkonstanten betragen fd(CO) = 15,86, fd(OsC) = 3,28, fd(OsI) = 1,13 mdyn/Å. Die Festigung der Os—C-Bindung durch stärkere Rückbindung in dem OsII(d6)-Komplex im Vergleich zur isostrukturellen OsIII(d5)-Verbindung wird diskutiert.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.199762301147