Attenuated Organomagnesium Activation of White Phosphorus

Abstract

Sequential reactions between a 2,6-diisopropylphenyl-substituted β-diketiminato magnesium n-butyl derivative and P4 allow the highly discriminating synthesis of unusual [nBu2P4]2− and [nBu2P8]2− cluster dianions.

Recent Developments in Homogeneous Organomagnesium Catalysis

“…[36] This stoichiometric transformationi sy et to be translated into ac atalytic process, buti ti sa ne nlighteningd emonstration of the innovative directions organomagnesium chemistry is headed. As ar esult of the redox-inactivity,e lementary steps in catalysis with both metal types primarily utilize s-bond metathesis andi nsertion.…”

Functionalization of P4 through Direct P−C Bond Formation

“…In 2015, Hill and co‐workers reported on the selective synthesis of the Mg 2+ ‐stabilized cluster dianion [ n Bu 2 P 4 ] 2− 15 from P 4 and β‐diketiminato n ‐butylmagnesium complex [( Dipp BDI)Mg n Bu] ( Dipp BDI=HC{C(Me)N(2,6‐ i Pr 2 C 6 H 3 )} 2 ; Scheme ) . The disubstituted P 4 ‐dianion likely results from initial formation of the [ n BuP 4 ] − butterfly anion [Eq.…”

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare‐Earth‐Metal Cyclo‐P3 Complexes

“…[1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization. [1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization.…”

“…The direct functionalization of white phosphorus (P 4 )t o construct value-added phosphorus-containing compounds is becoming ah ot area because it avoids the use of corrosive chlorine gas and the generation of large amounts of hydrochloric acid. [1][2][3][4][5][6] Fragmentation of P 4 is afundamental route to convert P 4 into activated intermediates,w hich enable subsequent functionalization. Basically,[2+ +2] fragmentation can yield the activated P 2 -containing species A or B,a nd [3+ +1] fragmentation can yield the activated P 1 -containing species or two possible P 3 -containing species C or D (Scheme 1a).…”