Characterization and Reactivity of the Tetrametallic Pd<sub>2</sub>-Mo<sub>2</sub> Complex Ph(Bu)P(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)Mo(CO)<sub>3</sub>Pd(μ-I)<sub>2</sub>PdMo(CO)<sub>3</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)P(Ph)Bu and Its Use to Model Pd-Catalyzed Cross-Coupling Rea
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The mechanism of the Pd-catalyzed cross-coupling reaction between tributyltin acetylides and metal iodides has been investigated with the use of a model Mo precursor bearing a ligand with appropriate steric and electronic properties. This study has allowed us to intercept the tetrametallic Pd2-Mo2 complex Ph(Bu)P(η5-C5H4)Mo(CO)3Pd(μ-I)2PdMo(CO)3(η5-C5H4)P(Ph)Bu, which is a precursor to the catalytically active solvento complex Ph(Bu)P(η5-C5H4)Mo(CO)3PdI(DMF). Both complexes play a key role in Pd-catalyzed cross-coupling reactions between tributyltin acetylides and metal iodides, leading to metal-σ-alkynyls. The catalytic cycle for such a reaction has been further elucidated, especially with regard to the role of the ligands in the metal iodide for the stabilization and/or detection of the intermediates as well as for the formation of the M-alkynyl product.
