Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XXXV [1]: Synthese und dynamisches Verhalten von Dicarbonyl[η5:1-(2-cyclopentadiendiyl)ethyl](η2-olefin)molybdän und -wolfram / Hindered Ligand Motions in Transition Metal Complexes, XXXV [1]: Synthesis and Dynamic Behaviour of Dicarbonyl[η5:1-(2-cyclopentadiendiyl)ethyl](η2-olefin)molybdenum and -tungsten
Open Access
- 1 October 1989
- journal article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung B
- Vol. 44 (10) , 1247-1259
- https://doi.org/10.1515/znb-1989-1018
Abstract
In order to investigate the coordination ability of quasi square pyramidal complexes, tricarbonyl[η5:1-(2-cyclopentadiendiyl)ethyl]molybdenum (1) and -tungsten (2) were reacted photochemically with ethylene (a), propene (b), 1-butene (c), Z-2-butene (d), E-2-butene (e), 2-methyl-propene (f), 2-methyl-2-butene (g), 2,3-dimethyl-2-butene (h), styrene (i), 2,2-dimethylcyclopropene (j), allene (k) and acetylene (I). 1 forms [Μο(η5:1-C5Η4C2H4)(CO)2(η2-olefin)] complexes with a—g, i, and k, 2 the corresponding tungsten complexes with a, g, h, and j as ligands. There is no reaction between 1 or 2 and acetylene. 1g and 2h represent the limits for complexes with sterically demanding olefin ligands and were detected only by IR spectroscopy. Prolongated UV irradiation of 2 and ethylene yields in addition to 2a [W(η5:1-C5H 4C2H4)(CO)(η2-C2H4)2] (2a′). Hindered olefin rotations around the metal-olefin bonds were detected for 1a—1c, 1e, 1f, 1i, and 2a with barrieres of activation between 50 to 75 kJ · mol-1.Keywords
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