HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES .40. SYNTHESIS AND DYNAMIC BEHAVIOR OF TRICARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE-TRIMETHYLPHOSPHITE-METAL(0) AND DICARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE-BIS(TRIMETHYLPHOSPHITE)-METAL(0) COMPLEXES OF CHROMIUM, MOLYBDENUM AND TUNGSTEN

Date

1992-06-01

Author

KREITER, CG
KOTZIAN, M
Özkar, Saim
ABUMOUR, I

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Tricarbonyl-eta-4-tricyclo[6.3.0.02.7]undeca-3,5-diene-trimethylphosphite-metal(0) and cis-dicarbonyl-eta-4-tricyclo[6.,3.0.02,7]undeca-3,5-diene-bis(trimethylphosphite)metal(0) complexes of chromium (1,4), molybdenum (2,5) and tungsten (3,6) have been prepared photochemically in high yields from the corresponding pentacarbonyl-trimethylphosphite-meta](0) or tetracarbonyl-bis(trimethylphosphite) metal(0) complexes, respectively, with tricyclo[6.3 .0.02,7 ]undeca-3,5-diene. The stereochemistry of 1-6 was determined by IR and NMR spectroscopy. In the case of tricarbonyl-eta-4-tricyclo[6.3.0.02,7] undeca-3,5-diene-trimethylphosphite-tungsten(0) (3), X-ray crystal and molecular structure analysis confirm the conclusions drawn from the spectroscopic data. The distorted pseudo-octahedral complexes 1-3 are obtained exclusively as f-isomers, and 4-6 as af-isomers. All of them show hindered ligand movements, according to their temperature-dependent NMR spectra. For 1-3 a. carbonyl scrambling, and for 4-6 a rotation of the diene ligand is observed.

URI

https://hdl.handle.net/11511/69990

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY

DOI

https://doi.org/10.1016/0022-328x(92)80115-e

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Department of Chemistry, Article

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HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES DECARBONYL (ETA-4-DIENE) TUNGSTEN(0) Özkar, Saim; KREITER, CG (1992-08-04) 1,2-Bis(dimethylphosphino)ethane-dicarbonyl-eta-4-diene-tungsten(0) complexes (diene = 1,3-butadiene (1), E-1,3-pentadiene (2), E,E-2,4-hexadiene (3) and E-2-methyl-1,3-pentadiene (4)) were synthesized by UV irradiation of 1,2-bis(dimethylphosphino)ethane-tetracarbonyltungsten(0) and the corresponding dienes in toluene. The constitutions of these complexes were determined by IR and NMR spectroscopy (H-1, C-13, P-31). The spectral data indicate pseudo-octahedral structures for the complexes. When the dienes ...
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Citation Formats

C. KREITER, M. KOTZIAN, S. Özkar, and I. ABUMOUR, “HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES .40. SYNTHESIS AND DYNAMIC BEHAVIOR OF TRICARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE-TRIMETHYLPHOSPHITE-METAL(0) AND DICARBONYL-ETA-4-TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE-BIS(TRIMETHYLPHOSPHITE)-METAL(0) COMPLEXES OF CHROMIUM, MOLYBDENUM AND TUNGSTEN,” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 159–170, 1992, Accessed: 00, 2021. [Online]. Available: https://hdl.handle.net/11511/69990.