HINDERED LIGANDS IN TRANSITION-METAL COMPLEXES .39. SYNTHESIS AND DYNAMIC BEHAVIOR OF TETRACARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE METAL(0) COMPLEXES AND DICARBONYL-BIS-(ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE METAL(0) COMPLEXES OF THE ELEMENTS CHROMIUM, MOLYBDENUM AND TUNGSTEN

Date

1992-05-01

Author

Özkar, Saim
KREITER, CG

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The hexacarbonyls of chromium, molybdenum, and tungsten react with tricyclo[6.3.0.0(2,7)]undeca-3,5-diene upon UV irradiation in a first step to tetracarbonyl-eta-4-tricyclo[6.3.0.0(2.7)]undeca-3,5-diene-chromium(0) (1), -molybdenum(0) (2) and -tungsten(0) (3). By longer irradiation, dicarbonyl-bis(eta-4-tricyclo[6.3.0.0(2.7)]undeca-3,5-diene)molybdenum(0) (4) and -tungsten(0) (5) are formed. The complexes were purified by chromatography and studied by IR, H-1, and C-13 NMR spectroscopy. The C-13 NMR signals of the CO ligands of 1-3 were found to be temperature dependent owing to a hindered CO scrambling. The H-1 and C-13 NMR signals of 4 and 5 are temperature dependent as well and indicate a hindered enantiomerization of the pseudo-octahedral complexes.

Subject Keywords

Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Materials Chemistry, Biochemistry

URI

https://hdl.handle.net/11511/70001

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY

DOI

https://doi.org/10.1016/0022-328x(92)83097-2

Collections

Department of Chemistry, Article

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HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES .45. STRUCTURE AND DYNAMIC BEHAVIOR OF CIS-DICARBONYL-BIS(ETA(4)-1,3-DIENE)CHROMIUM(0), CIS-DICARBONYL-BIS(ETA(4)-1,3-DIENE)MOLYBDENUM(0) AND CIS-DICARBONYL-BIS(ETA(4)-1,3-DIENE)TUNGSTEN(0) COMPLEXES Özkar, Saim; KOTZIAN, M (Elsevier BV, 1995-05-01) The static and dynamic stereochemistry of cis-bis(eta(4)-1,3-butadiene)dicarbonyl-molybdenum(0)(1) and -tungsten(0)(2), as well as of cis-dicarbonyl-bis(eta(4)-1,3-cyclodexadiene)chromium(0)(3), -molybdenum(0)(4) and -tungsten(0)(5) was studied by IR and NMR spectroscopy. The complexes 1-5 show temperature-dependent NMR spectra, according to hindered ligand movements. In the case of 1, the crystal and molecular structure were determined by an X-ray diffraction analysis.
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) KOTZIAN, M; KREITER, CG; MICHAEL, G; Özkar, Saim (Wiley, 1983-01-01) 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 (LP(CH3)3 1A–6A; LP(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) for...
Friedel-Crafts alkylation of ferrocene with Z-cyclooctene and cyclohexene Grevels, Friedrich-Wilhelm; KURAN, Ayla; Özkar, Saim; Zora, Metin (Elsevier BV, 1999-09-15) Cycloalkylated ferrocene derivatives, potentially useful as liquid burning rate modifiers for the HTPB/AP-based composite rocket propellants, were synthesized by the Friedel-Crafts alkylation of ferrocene with Z-cyclooctene or cyclohexene in the presence of AlCl3 as a Lewis acid catalyst. The reaction with Z-cyclooctene yields a mixture of main products containing up to four C8H15 substituents, each of which exists in several isomeric forms, as recognized by MS and GC-MS techniques. Two isomeric monosubstit...
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Citation Formats

S. Özkar and C. KREITER, “HINDERED LIGANDS IN TRANSITION-METAL COMPLEXES .39. SYNTHESIS AND DYNAMIC BEHAVIOR OF TETRACARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE METAL(0) COMPLEXES AND DICARBONYL-BIS-(ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE METAL(0) COMPLEXES OF THE ELEMENTS CHROMIUM, MOLYBDENUM AND TUNGSTEN,” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 345–351, 1992, Accessed: 00, 2021. [Online]. Available: https://hdl.handle.net/11511/70001.