Reaction of [(PPh3)3RuCl2] with white phosphorus: synthesis of the first RuII complex featuring a tetrahedro-tetraphosphorus ligand

Metal-Mediated Degradation and Reaggregation of White Phosphorus

“…The reaction of the hydrogenation catalyst [(PPh 3 ) 3 RuCl 2 ] with white phosphorus in toluene was briefly investigated by Peruzzini et al during a study aimed at exploring the possibility of hydrogenating P 4 homogeneously [23]. Notwithstanding that systems capable of accomplishing the hydrogenation of elemental phosphorus have not yet been individuated [4,5], the reaction resulted in the formation of [(PPh 3 ) 2 RuCl(m-Cl) 3 Ru(PPh 3 ) 2 (h 1 -P 4 )] (11) which has been the first dinuclear species containing a monohapto-P 4 ligand (Eq.…”

“…Although the paucity of the collected data should be critically considered; nevertheless some meaningful conclusions can be drawn. Thus, it appears that the metallated P A atom experiences the larger downfield shift with respect to free P 4 with D-values ranging from about 100 ppm for the tungsten(0) derivatives [W(CO) 3 (PR 3 ) 2 (h 1 -P 4 )] (5, 6) [16], to more than 200 ppm for the ruthenium(II) complex [(PPh 3 ) 2 RuCl(m-Cl) 3 Ru(PPh 3 ) 2 (h 1 -P 4 )] (11) [23]. In contrast, the three magnetically equivalent P B atoms show a less pronounced shift with a narrow distribution of values [d(P B ) ave = -478].…”

P4 Activation with Pt0 Metal Centers: Selective Formation of a Dinuclear {Pt2(μ,η2:2‐P2)} Complex

“…[11] Most importantly, these "P 2 " fragments have been trapped by cyclohexadiene to form phosphorus containing tetracyclic species, rare examples of functionalization under very mild conditions. [11,12] We present here the use of 14-electron complexes of Pt 0 that simultaneously provide two sites of coordination and a d 10 configuration, which result in a strong activation of P 4 . We show that the use of a bidentate diphosphine ligand (vs. two phosphines) allows the isolation of a novel dinuclear…”

“…[2] However, almost all the early studies after this date used harsh conditions (thermal or photochemical) resulting in unpredictable P 4 fragmentation. [3] It was later recognized that carefully designed transition-metal precursors, which provide a single coordination site under "soft conditions" could lead to h 1 coordination of P 4 , which in this case acts as a "typical" phosphine ligand. [4] In particular; Peruzzini et al have studied extensively the reactivity of Ru complexes of such h 1 derivatives, and shown possible functionalization.…”

“…[3] It was later recognized that carefully designed transition-metal precursors, which provide a single coordination site under "soft conditions" could lead to h 1 coordination of P 4 , which in this case acts as a "typical" phosphine ligand. [4] In particular; Peruzzini et al have studied extensively the reactivity of Ru complexes of such h 1 derivatives, and shown possible functionalization. [5] On the other hand, when two coordination sites are made available, insertion of the metal center in a PÀP bond is typically observed, resulting in the formal oxidation of the metal center, and concomitant reduction of P 4 .…”