White Phosphorus is largely used to produce organophosphorus compounds which are key materials for several industrial applications. The manufacturing of these useful compounds is still based on an obsolete and energy intensive technology, i.e. the environmentally poor route encompassing the direct chlorination of P4 to PCl3 generally followed by PCl3 alkoxydation. As a result, esters of the different oxyacids are produced.Any implementation of the above process which directly (and possibly catalytically) transforms white phosphorus into valuable organophosphorus compounds is therefore worth pursuing. A fundamental step towards this goal is the unraveling of the elementary steps which bring about the formation of P-heteroatom bonds, such as P-H (P4-hydrogenation) and P-O bond (P4-alkoxydation) occurring in the coordination sphere of active transition metal species.The lecture will focus on the astonishing reactivity of Ru-coordinated P4 with water which results in the stepwise formation of PH3, H3PO3, H3PO2 and the elusive oxide PH3O. Hydroxopolyphosphine chains including four, three or two P-atoms, may be also easily achieved together with rare examples of polyphosphorus hydrides which have been trapped as a bridging ligand between two LnRu moieties.Some of them, i.e. P4H2, may be considered as the initial step on the way of the long searched hydrogenation of elemental phosphorus.MP thanks the project RFP7-PEOPLE-2012-ITN - 317404 'A European Training Network for Sus tainable Phos phorus Chemistry (SUSPHOS )'.

Unraveling the mechanism of the ruthenium assisted hydrolysis of white phosphorus

247th National Meeting (2014)

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