Organorheniumhalogenide: Synthesen, Strukturen und Reaktivität gegenüber Alkinen / Organorhenium Halogenides: Synthesis, Structure and Reactivity upon Treatment with Alkynes
Open Access
- 1 November 1988
- journal article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung B
- Vol. 43 (11) , 1391-1404
- https://doi.org/10.1515/znb-1988-1104
Abstract
The organorhenium(V) complexes (η5-C5Me5)ReX4 (2a, X = Cl; 2b, X = Br; Me = CH3) undergo stepwise dehalogenation upon treatment with various reducing agents, e.g. with HgCl2-activated aluminium powder, forming the isolable ReIV and ReIII dimers [η5-C5Me5)ReCl3]2 (3a) and [η5-C5Me5)ReX2]2 (4a, X = Cl;4b, X = Br), respectively. The weak metal-metal single bond of 3a (307.4(0) pm; X-ray diffraction study) is disrupted upon reaction with alkynes yielding the ReIII derivatives (η5-C5Me5)ReCl2(η2-R1CCR2) (9a-e; R1, R2: alkyl, aryl) and novel rhenium(V)- allylidenyl complexes of type (η5-C5Me5)ReCl2[η1:η3-R1CC(Cl)CHR3] (10a-d; R1: alkyl. aryl; R3: H, alkyl). Reduction of 2a (Al/HgCl2) in the presence of alkynes gives a complex reaction mixture of 9a-c, 10a - c and bis(π-alkyne) complexes [(η5-C5Me5)ReCl(η2-R1CCR2)2] + [AlCl4]-(11a-c) (X-ray diffraction study of the related derivative [(η5-C5Me5)ReBr(η2-MeCCMe)2] + [SbF6]-).Keywords
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