An Unexpected Pathway in the Cage Opening and Aggregation of P₄

Abstract

Graceful degradation: The reaction of the [(Me3Si)3Si]− ion with white phosphorus results in a new phosphorus‐based dianion (see scheme; R=Si(SiMe3)3), apparently arising from the unexpected aggregation of two [RP4]− units into a P7 nortricyclic core with an exo anionic P atom. The formation of this dianion sheds new light on the mechanism(s) of P4 degradation by nucleophiles and the ability of silyl substituents to direct product formation.

Heptaphosphanortricyclenes with Oligosilyl Substituents: Syntheses and Reactions

“…[22,23] It is worth mentioning that substituted P 7 systems such as [HypP 7 (PHyp)] 2-are formed in the treatment of white phosphorus with KSi(SiMe 3 ) 3 . [24] Results and Discussion…”

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

“…41 Yet another unique P 6 ligand geometry has been provided by Wolczanski and coworkers who found that if a reaction mixture containing ( t Bu 3 SiO) 3 NbPMe 3 and P 4 was allowed to incubate at −78 • C for 7 h, followed by slow warming to 23 • C, then the red P 6 -complex, (( t Bu 3 SiO) 3 Nb) 2 (µ 2 :η 2 ,η 2 -c P 3 -c P 3 ), 51, could be isolated in 77% yield. 34 In 51, two of the niobium-phosphorus distances of 2.559 (8) 67 What distinguished the octaphosphorus cluster in 52 from other related structural motifs seen in polyphosphorus ligands derived from P 4 was the fact that it incorporated a metal-phosphinidene bond, the reactivity of which was exploited, in one instance through phospha-Wittig chemistry. 61 Another example of ostensible P 4 dimerization comes from the lab of Roesky and coworkers who found that diffusion of P 4 vapor into a toluene solution of solvate-free permethyl samarocene, Cp* 2 Sm, over a period of several days resulted in the formation of (Cp* 2 Sm) 4 P 8 (53) as red crystals.…”

Attenuated Organomagnesium Activation of White Phosphorus

“…Wright and co-workers described the synthesis of the [R 2 P 8 ] 2− cluster dianion ( 4 ) derived from a {P 7 } 3− Zintl ion core through the reaction of the very bulky hypersilyl potassium reagent with P 4 . [8] The disubstituted butterfly compound 5 (Mes*=2,4,6- t Bu 3 C 6 H 2 ) and the diphosphene Mes*P=PMes* were similarly isolated from the reaction of Mes*Li and P 4 in the presence of Mes*Br. [9] Production of compound 5 presumably occurs through initial addition of Mes*Li across a P–P bond within the P 4 unit and the intermediacy of the consequent organopolyphosphorus anion.…”