Fragmentation, catenation, and direct functionalisation of white phosphorus by a uranium()-silyl-phosphino-carbene complex

Room temperature reaction of the uranium( iv )-carbene [U{C(SiMe 3 )(PPh 2 )}(BIPM TMS )(μ-Cl)Li(TMEDA)(μ-TMEDA) 0.5 ] 2 ( 1 , BIPM TMS = C(PPh 2 NSiMe 3 ) 2 ) with white phosphorus (P 4 ) produces the organo-P 5 compound [P 5 {C(SiMe 3 )(PPh 2 )} 2 ][Li(TMEDA) 2 ] ( 2 ) and the uranium( iv )-methanediide [U{BIPM TMS }{Cl}{μ-Cl} 2 {Li(TMEDA)}] ( 3 ). This is an unprecedented example of cooperative metal-carbene P 4 activation/insertion into a metal-carbon double bond and also an actinide complex reacting with P 4 to directly form an organophosphorus species. Conducting the reaction at low temperature permits the isolation of the diuranium( iv ) complex [{U(BIPM TMS )([μ-η 2 :η 2 -P 2 ]C[SiMe 3 ][PPh 2 ])} 2 ] ( 4 ), which then converts to 2 and 3 . Thus, surprisingly, in contrast to all other actinide P 4 reactivity, although this reaction produces catenation overall it proceeds via P 4 cleavage to functionalised P 2 units. Hence, this work establishes a proof of concept synthetic cycle for direct fragmentation, catenation, and functionalisation of P 4 . Unprecedented insertion of P 4 into a M&z.dbd;C double bond is reported, revealing overall catenation via P 4 -fragmentation into R 2 CP 2 units.