Heteropolymetallic Complex Syntheses by Reiterative Nucleophilic Additions of Lithiated (η6-Arene)tricarbonylchromium Compounds to Cationic (η6-Benzene)manganese Complexes

Treatment of lithiated (η6-Xn-substituted-arene)Cr(CO)3 complexes (X = OMe, n = 2, 3) with (η6-benzene)Mn(CO)xL3-x PF6 complexes (L = P(OEt)3, x = 0, 1) gave rise to the formation of di-, tri-, and tetrapolymetallic complexes depending on the experimental conditions. A “one-pot” procedure was developed to obtain tetranuclear complexes directly from (η6-arene)Cr and -Mn mononuclear complexes. The molecular structures of the trinuclear complex 5b ((CO)3Cr[(μ-η6-1,3-(OCH3)2-C6H2:(η5-C6H6)2]Mn2[(CO)4(P(OEt)3)2] and of tetranuclear complex 9 ((CO)3Cr[μ-η6-1,3,5-(OCH3)3-C6:(η5-C6H6)3]Mn3[(CO)6(P(OEt)3)3] have been determined by X-ray crystallography.