Abstract
Zusammenfassung The organorhenium(V) complex (η5-C5Me5)ReCl4(1; Me CH3) undergoes stepwise dechlorination upon treatment with HgCl2-activated aluminum powder, thus forming the isolable ReIV and ReIII dimers [(η5-C5Me5)ReCl3]2 (2) and [(η5-C5Me5)ReCl2]2 (3), respectively. These reductions are reversible when 3 and 2 react with chlorine. The short metal-metal distance of the diamagnetic compound 3 (250.6( 196.1(3) 196.9(3) pm) and exhibiting a strong trans influence at the π-bonded ring ligand. Stepwise alkylation of 4 using methylmagnesium chloride gives the methyl complexes of composition (η5-C5Me5)Re(CH3)Cl(η2-EtCCEt) (5) and (η5-C5Me5)Re(CH3)2(η2-EtCCEt) (6) while hydrolysis of 4 yields the oxo-derivative (η5-C5Me5)ReO(η2-EtCCEt) (7).
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