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UV-irradiation of decacarbonyl-dirhenium(0) (1) and acetylene in hexane yields a mixture of complexes, which were separated by preparative HPL-chromatography and characterized by elemental analysis, IR, NMR and mass spectroscopy. Main product of the reaction is octa- carbonyl-μ-(η 2:1 -ethynyl)-μ-hydrido-dirhenium(I) (4). Tricarbonyl-η 5 -methylcyclopentadienyl- rhenium(I) (2) and tetracarbonyl-2-3:9-η-(8,10-dinorborna-2,5-dien-9-yl)-rhenium(I) (3) are ob­tained in moderate yields. Minor by-products of the reaction are octacarbonyl-μ-hydrido-μ-η 2:1 - vinyl-dirhenium(I) (5), tridecacarbonyl-μ-η 2:1 -vinyl-trirhenium (6) and HRe 3 (CO) 14  (7). 4 shows a hindered ligand movement of the η 2:1 -ethynyl bridge, with ⊿G ≠  250  =  48.2 kJ · mol -1 .

zeitschrift für naturforschung b

Gehinderte Ligandenbewegungen in Übergangsmetallkomplexen, XXII [1]. Synthese und Moleküldynamik von OctacarbonyI-μ-(η 2:1 -ethinyl)-μ-hydrido-dirheniuni(I) / Hindered Ligand Movements in Transition Metal Complexes, XXII [1]. Synthesis and Molecule Dynamics of Octacarbonyl-μ-(η 2:1 -ethynyl)-μ-hydrido-dirhenium(I)