Heteropolymetallic Complex Syntheses by Reiterative Nucleophilic Additions of Lithiated (η<sup>6</sup>-Arene)tricarbonylchromium Compounds to Cationic (η<sup>6</sup>-Benzene)manganese Complexes

Treatment of lithiated (η<sup>6</sup>-X<i><sub>n</sub></i>-substituted-arene)Cr(CO)<sub>3</sub> complexes (X = OMe, <i>n</i> = 2, 3) with (η<sup>6</sup>-benzene)Mn(CO)<i><sub>x</sub></i>L<sub>3</sub><sub>-</sub><i><sub>x</sub></i> PF<sub>6</sub> complexes (L = P(OEt)<sub>3</sub>, <i>x</i> = 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 (η<sup>6</sup>-arene)Cr and -Mn mononuclear complexes. The molecular structures of the trinuclear complex <b>5b</b> ((CO)<sub>3</sub>Cr[(μ-η<sup>6</sup>-1,3-(OCH<sub>3</sub>)<sub>2</sub>-C<sub>6</sub>H<sub>2</sub>:(η<sup>5</sup>-C<sub>6</sub>H<sub>6</sub>)<sub>2</sub>]Mn<sub>2</sub>[(CO)<sub>4</sub>(P(OEt)<sub>3</sub>)<sub>2</sub>] and of tetranuclear complex <b>9</b> ((CO)<sub>3</sub>Cr[μ-η<sup>6</sup>-1,3,5-(OCH<sub>3</sub>)<sub>3</sub>-C<sub>6</sub>:(η<sup>5</sup>-C<sub>6</sub>H<sub>6</sub>)<sub>3</sub>]Mn<sub>3</sub>[(CO)<sub>6</sub>(P(OEt)<sub>3</sub>)<sub>3</sub>] have been determined by X-ray crystallography.