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HINDERED LIGAND MOTIONS IN TRANSITION-METAL COMPLEXES .18. SYNTHESIS AND DYNAMIC BEHAVIOR OF TRICARBONYL(ETA-DIENE)(TRIMETHYLPHOSPHANE)CHROMIUM(0) AND TRICARBONYL(ETA-DIENE)(TRIMETHYL PHOSPHITE)CHROMIUM(0)
Date
1983-01-01
Author
KOTZIAN, M
KREITER, CG
MICHAEL, G
Özkar, Saim
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Irradiation of Cr(CO)5[P(CH3)3] or Cr(CO)5[P(OCH3)3] in presence of 1,3‐butadiene (1), trans‐1,3‐pentadiene (2), and 2‐ethyl‐1,3‐butadiene (3), trans, trans‐2,4‐hexadiene (4), 2‐methyl‐1,3‐pentadiene (5), and 2‐ethyl‐1,3‐butadiene (6) produces in good yields Cr(CO)3L(η4‐diene) complexes (LP(CH3)3 1A–6A; LP(OCH3)3 1B–6B). The configurations of these complexes were determined by IR and NMR spectroscopy (1H, 13C, 31P). Cr(CO)3[P(OCH3)3](η4‐1,3‐pentadiene) (2B) and Cr(CO)3[P(OCH3)3](η4‐2,4‐hexadiene) (4B) form a mixture of two possible facial stereoisomers a and f. The other complexes favour only the a‐form. 2B and 4B show two different, intramolecular hindered ligand movements: Isomerization of the a‐ and f‐forms and carbonyl scrambling. Carbonyl scrambling is also observed for all the other complexes. The barriers of activation of these movements are around 40 and 50 kJ. mol−1, respectively. Transition states of trigonal prismatic geometries are suitable models to explain these movements.
Subject Keywords
Inorganic Chemistry
URI
https://hdl.handle.net/11511/69982
Journal
CHEMISCHE BERICHTE-RECUEIL
DOI
https://doi.org/10.1002/cber.19831161113
Collections
Department of Chemistry, Article
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M. KOTZIAN, C. KREITER, G. MICHAEL, and S. Özkar, “HINDERED LIGAND MOTIONS IN TRANSITION-METAL COMPLEXES .18. SYNTHESIS AND DYNAMIC BEHAVIOR OF TRICARBONYL(ETA-DIENE)(TRIMETHYLPHOSPHANE)CHROMIUM(0) AND TRICARBONYL(ETA-DIENE)(TRIMETHYL PHOSPHITE)CHROMIUM(0),”
CHEMISCHE BERICHTE-RECUEIL
, pp. 3637–3658, 1983, Accessed: 00, 2021. [Online]. Available: https://hdl.handle.net/11511/69982.