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

ABSTRACT: 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.

SUBMITTER: Yadav R 

PROVIDER: S-EPMC8518058 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature