| | 2 | Author
| CorneliusG. Kreiter, Wolfgang Michels, Reiner Exner | Requires cookie* | | | Title
| Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XXXVII [1]: Photoreaktion von Dekacarbonyldirhenium mit Phenylallen Hindered Ligand M otions in Transition Metal Complexes, XXXVII [1]: Photoreaction of Decacarbonyldirhenium with Phenylallene  | | | | Abstract
| Decacarbonyldirhenium (1) and phenylallene (2) form upon U V irradiation four dinuclear complexes: Decacarbonyl-//-^l:l-(3,4-diphenyl-1,5-hexadien-2,5-diyl)-dirhenium (3), ennea-carb on yl-//V :3-(3-phenyl-2-propen-l,2-diyl)-dirhenium (4), octacarb on yl-//-h yd rid o-/iV 2-(3-phenyl-l,2-propadien-l-yl)-dirhenium (5) and octacarbonyl-/i-?72 2-(phenyl-l,2-propa-diene)-dirhenium (6). The thermolabile complex 4 looses CO and forms the phenylallene bridged compound 6. Similarly 5 is rearranged to 6 by transfer o f the hydrido ligand to the 3-phenyl-1,2-propadien-l-yl bridge. The formation o f 3 and 4 can be rationalized via pentacar-bonyl-phenylpropenediyl-rhenium radicals which dimerize to give 3 or add pentacarbonyl-rhenium radicals, loose CO and form 4. The crystal and molecular structure o f 3 was deter mined by X-ray structure analysis. In the solid state the molecule is present in the ± ap confor mation. In solution at 233 K the ± a p , +sc, and -s c conform ations are equally populated. By a hindered rotation around a CC single bond, the three conformers are interconverted with a rotation barrier o f J G * 25g = 52.3 ± 1 k J -m o L 1. | | | |
Reference
| Z. Naturforsch. 45b, 793—8 (1990); eingegangen am 3. Januar 1990 | | | |
Published
| 1990 | | | |
Keywords
| Decacarbonyldirhenium, Photoreaction, Phenylallene, Ligand Properties | | | |
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| default:Reihe_B/45/ZNB-1990-45b-0793.pdf | | | | Identifier
| ZNB-1990-45b-0793 | | | | Volume
| 45 | |
| 3 | Author
| CorneliusG. Kreiter, Wolfgang Michels, Gerhard Heeb | Requires cookie* | | | Title
| Photoreaktionen von Dekacarbonyldirhenium mit A llen und unverzweigten Allenderivaten Photoreactions of Decacarbonyldirhenium with Allene and Unbranched Derivatives o f Allene | | | | Abstract
| Decacarbonyldirhenium (1) reacts upon U V irradiation with allene (2), 1,2-butadiene (3) and 2,3-pentadiene (4) preferentially by CO substitution and oxidative rearrangement to the corresponding enneacarbonyl-//-?/1:3-endiyl-dirhenium complexes 5, 9, and 15 and to the octacarbonyl-,«-//-:2-allene-dirhenium complexes 6, the stereoisomers 10, 11, and 16. A t ele vated temperature 5, 9, and 15 loose CO and yield by a reductive rearrangement also the complexes 6, 10, 11, and 16. In addition to these main products, depending upon the allene derivative used, various by-products are obtained. By-products of the reaction o f 1 with 2 are octacarbonyl-M-/73:3-(2,3-dimethylene-buta-l,4-diyl)dirhenium (7) and ^-^^-allene-hexacarbonyl-/!-//1:3-i-propene-l,3-diyl-dirheniurn (8). The photo reaction of 1 with 3 yields, in addition to 9-11 , tetracarbonyl-^3-(£'-5-ethylidene-4-methyl-2-cyclopenten-l-yl)rhenium (12) | | | |
Reference
| Z. Naturforsch. 50b, 649—660 (1995); eingegangen am 28. September 1994 | | | |
Published
| 1995 | | | |
Keywords
| Decacarbonyldirhenium, Photoreaction, Allene, Derivatives, Complexes | | | |
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| default:Reihe_B/50/ZNB-1995-50b-0649.pdf | | | | Identifier
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| 50 | |
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