The treatment of representative (η6-arene)tricarbonylchromium(0) complexes 1a–c and 4 with 3 equivalents of LiTMP followed by an electrophilic quench with Me3SiCl provided a series of trisilylated complexes 2a–c and 5a. The use of Me3SnCl and Ph2PCl as electrophile also yielded unusual trisubstituted complexes 13a and 13b. The X-ray crystallographic structure of complex 13b is reported. Deuteration studies using deuteroacetic acid as the electrophile led to the observation of a trideuterated species presumably derived from a trianionic species formed during the reaction. Efficient disubstitution was observed when complexes 7, 9 and 11 were treated with 3 equivalents of LDA followed by an electrophilic quench with Me3SiCl
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