New Adventures in the Molecular Chemistry of Phosphorus

摘要

"Phosphorus Remains Exciting!" was the title of a recent Highlight by Pfitzner that focused on developments in the solid-state chemistry of the element. The same conclusion may also be drawn with regard to the molecular chemistry of phosphorus. Important developments have been reported in the chemistry of low-coordination phosphorus, where Cummins described elegant procedures whereby phosphorus-containing moieties were assembled on transition-metal scaffolds starting from terminal metal-phosphide or nitride functionalities. By investigating the reactivity of these species, a preparation of P2 under mild conditions was discovered; this has been exploited by observations of its reactivity towards both organic and inorganic systems. In addition, interesting developments in phosphorus-rich cage complexes have developed from some of the above work; it should be noted that related cages have also been observed by using different strategies. By using a similar approach of manipulation of a main group unit in the protective sphere of a transition metal, Griitzmacher and co-workers removed the silyl group of a P-bonded silylphosphaalkyne group attached to a ruthenium center by reaction with a nucleophile, thus leading to a metal complex of the cyaphide anion.'5' This result opens the possibility of exploring the chemistry of this heavier homologue of the cyanide anion.