Spectroscopic studies of 4-substituted pyridinium 2-pyridylcarbonylmethylide-rhodium(I) complexes and x-ray molecular structure of (1,5-cyclooctadiene) (4-methylpyridinium 2-pyridylcarbonylmethylide)rhodium(I) perchlorate |
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Authors: | Gen-etsu Matsubayashi Seigo Akazawa |
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Institution: | Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565, Japan |
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Abstract: | (1,5-Cyclooctadiene) (4-substituted pyridinium 2-pyridylcarbonylmethylide)- rhodium(I) perchlorates, Rh(COD)(C5H4NC(O)C?H+C5H4X-4)]ClO4 COD = 1,5-cyclooctadiene; X = CH3C(O), CH3OC(O), C6H5, CH3, and H], have been prepared. They are shown to have the geometry with coordination by the pyridyl nitrogen and carbonyl oxygen atoms of the ylide ligands and to exhibit intramolecular rearrangement of coordinated COD in chloroform, methanol, and dimethyl sulphoxide based on IR and 1H NMR spectroscopies. Although the ylides have exhibited fluorescence bands due to an intramolecular charge-transfer transition and phosphorescence bands due to a carbonyl 3(n?π*) transition, the complexes have given emission bands due to the metal-to-ylide ligand charge-transfer transition. A.single crystal X-ray crystal structure has been determined for Rh(COD)(C5H4NC(O)C?H+C5H4CH3-4)]ClO4. The crystals are monoclinic, space group P21/n with cell dimensions a = 14.887(3), b = 20.274(4), c = 6.966(1) Å, β = 96.13(1)°, and Z = 4. The structure has been refined by a block-diagonal least-squares method to final R = 0.060 for 2997 independent reflections with |Fo| > 3σ(F). The ylide carbon-pyridinium nitrogen bond distance is 1.420(10) Å. The bonded distances from rhodium to the midpoints of the double bonds of COD are 1.982(11) and 2.014(12) Å. |
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Keywords: | Author to whom correspondence should be addressed |
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