A Structural Diversity of Molecular Alkaline-Earth-Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion.

A series of molecular group 2 polyphosphides has been synthesized by using air-stable [Cp*Fe(η5 -P5 )] (Cp*=C5 Me5 ) or white phosphorus as polyphosphorus precursors. Different types of group 2 reagents such as organo-magnesium, mono-valent magnesium, and molecular calcium hydride complexes have been investigated to activate these polyphosphorus sources. The organo-magnesium complex [(Dipp BDI-Mg(CH3 ))2 ] (Dipp BDI={[2,6-i Pr2 C6 H3 NCMe]2 CH}- ) reacts with [Cp*Fe(η5 -P5 )] to give an unprecedented Mg/Fe-supramolecular wheel. Kinetically controlled activation of [Cp*Fe(η5 -P5 )] by different mono-valent magnesium complexes allowed the isolation of Mg-coordinated formally mono- and di-reduced products of [Cp*Fe(η5 -P5 )]. To obtain the first examples of molecular calcium-polyphosphides, a molecular calcium hydride complex was used to reduce the aromatic cyclo-P5 ring of [Cp*Fe(η5 -P5 )]. The Ca-Fe-polyphosphide is also characterized by quantum chemical calculations and compared with the corresponding Mg complex. Moreover, a calcium coordinated Zintl ion (P7 )3- was obtained by molecular calcium hydride mediated P4 reduction.