The lecture will summarize the most recent achievements in the area of transition metal-mediated reactivity of elemental phosphorus deriving from the authors' own research at ICCOPM-CNR Florence. Highlights of the presentation will include:
• the metal-mediated activation of white phosphorus with particular emphasis to the unusual hydrolytic behavior of the P4 molecule following its η1-coordination to a metal centre (Fe, Ru, Os), which affords a variety of organometallic compounds stabilizing unusual low-valent phosphorus species as ligands;1
• the high pressure reactivity of red phosphorus with water and other small molecules;2
• some preliminary results dealing with the chemistry of the less reactive allotrope of the element, i.e. black phosphorus,3 including the easy access to 2D-flakes of phosphorene (the all-P counterpart of graphene) via a solution synthesis which avoids the use of the boring and scarcely productive scotch-tape exfoliation method and its reactivity with organometallic synthons.
Acknowledgments: MP thanks all the coworkers listed in the references. Thanks are expressed to EC through the SUSPHOS grant RFP7-PEOPLE-2012-ITN - 317404 and to the European Research Council for funding the project PHOSFUN "Phosphorene functionalization: a new platform for advanced multifunctional materials”(GA No. 670173) through an ERC Advanced Grant).
References:
[1] P. Barbaro, C. Bazzicalupi, M. Peruzzini, S. Seniori Costantini, P. Stoppioni Angew. Chem. Int. Ed. 2012, 51, 8628 - 8631, and references therein.
[2] M. Ceppatelli, R. Bini, M. Caporali, M. Peruzzini
Angew. Chem. Int. Ed. 2013, 52, 2313 –2317.
[3] M. Serrano-Ruiz, M. Caporali, A. Ienco, V. Piazza, S. Heun, M. Peruzzini, Adv. Mater. Interfaces, 2015, 2, 1400225. DOI: 10.1002/admi.201400225.
P - Advanced synthesis and characterization , P - Reactions of coordination compounds , P - General aspects of inorganic chemistry
