Synthesis and Reactivity of a Cyclooctatetraene-Like Polyphosphorus Ligand Complex [Cyclo-P₈ ]

The thermolysis of Cp'''Ta(CO)₄ with white phosphorus (P₄ ) gives access to [{Cp'''Ta}₂ (μ,η^{2 : 2 : 2 : 2 : 1 : 1} -P₈ )] (A), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P₈ ligand. While ring sizes of n >6 have remained elusive for cyclo-P_n structural motifs, the choice of the transition metal, co-ligand and reaction conditions allowed the isolation of A. Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp'''Ta}₄ (μ₄ ,η^{2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1} -P₁₆ )][TEF]₂ (4, TEF=[Al(OC{CF₃ }₃ )₄ ]^- ). Reduction, however, leads to the fission of one P-P bond in A followed by rapid dimerization to form [K@[2.2.2]cryptand]₂ [{Cp'''Ta}₄ (μ₄ ,η^{2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1} -P₁₆ )] (5), which features an unprecedented chain-type P₁₆ ligand. Lastly, A serves as a P₂ synthon, via ring contraction to the triple-decker complex [{Cp'''Ta}₂ (μ,η^6 : 6 -P₆ )] (B).