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Chemically inert oxidometal(V) corrols of molybdenum and rhenium undergo clean ligand-exchange reactions upon the action of SiCl4. The resulting dichlorido complexes show trigonal prismatic coordination of the metal ion with the chlorine atoms residing in a cis configuration, and were studied by optical and resonance spectroscopy as well as DFT calculations. In situ reactivity studies with carbon nucleophiles indicate high reactivity for chlorine replacement. Treatment with sodium cyclopentadienide paves the way to robust molybdenum corrolocene half-sandwich complexes. These organometallic compounds are the first corrole species that stabilize an air-stable and diamagnetic low spin d2-MoIV center. Structural, spectroelectrochemical, and chemical investigations prove a reversible MoIV/MoV redox couple close to the Fc/Fc+ potential for these systems. The high stability of the compounds in both redox states calls for future applications in catalysis and as redox switch. [ABSTRACT FROM AUTHOR]