White phosphorus is the most notable allotrope of elemental phosphorus in terms of reactivity and represents the entry point for the synthesis of organophosphorus compounds (OCPs). Substantial efforts have been devoted to the development of direct P4 functionalization  to escape the traditional stages via the intermediacy of PCl3 and subsequent transformation reactions. In this respect we are developing general protocols for the formation of cationic phosphorus cages by consecutive insertion of phoshenium cations[1] into P-P bonds of P4 to form monocationic cages of the type [R2P5]+, [RP5Cl]+ and [P5Cl2]+ (R = alky, aryl, NR2) as well as dicationic [R4P6]2+ and tricationic [R6P7]3+ species.[2,3] Recently, we have been able to stepwise breakdown our cationic [RP5Cl]+ (R = Dipp) cages by the nucleophilic reaction with NHCs (N-heterocyclic carbenes) into ligand-stabilized cationic [P4]2+, [P3]+, and [P2]+ fragments which represent novel building blocks  .[4] The obtained compounds display new bonding situations which will be discussed in detail. References: [1]         Weigand, J. J.; Burford, N.; Decken, A.; Schulz, A. Eur. J. Inorg. Chem., 2007  , 4868.[2]          Weigand, J. J.; Holthausen, M. H.; Fr�hlich, R. Angew. Chem. Int. Ed. 2009  , 48, 295.[3]          Weigand, J. J.; Holthausen, M. H. J. Am. Chem. Soc. 2009  , 131, 14210.[4]          Holthausen, M. H.; Richter, R.; Hepp, A.; Weigand, J. J. Chem. Commun. 2010  , 46, 6921.

Novel NHC-stabilized polyphosphorus cations from P4 functionalization

243rd National Meeting (2012)

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