Synthesis of a Silylated Phosphorus Biradicaloid and Its Utilization in the Activation of Small Molecules

Abstract

Reduction of silylated 1,3-dichloro-1,3-diphospha-2,4-diazane, [ClP(μ-NHyp)] 2 [Hyp = Si(SiMe 3 ) 3 ], with activated magnesium in dimethoxyethane allowed the isolation and full characterization of the first stable silylated biradicaloid, [P(μ- [a]

Dichloro‐Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry

“…This weakening of one P−Cl bond emphasizes the instability of compound 10Mes* with respect to the previously discussed isomerization reactions. Also, the electronic situation is in contrast to related compounds of heavier pnictogens such as TerNNN(ECl 2 )Ter (E=P, As, Sb, Bi), TerNPN(SbCl 2 )Ter or TerPAsN(SbCl 2 )Ter, where the coplanar σ *(P−Cl) orbital acted as a σ acceptor for the in‐plane LP at the opposite N or P atom …”

Magnesium(I) Halide versus Magnesium Metal: Differences in Reaction Energy and Reactivity Monitored in Reduction Processes of P−Cl Bonds

“…Therefore, we investigated the reduction process of phosphor halogen bonds with 1 . The classical reduction of phosphorus–halogen bonds with Mg metal has been described many times: for example, reductive dehalogenation reactions of chlorophosphines with yields up to 85 % in special cases has been described …”

“…The chemistry of dichloro‐cyclodiphosphadiazanes [ClP(μ‐NR)] 2 , which were first discovered in 1894, has been investigated to quite some extent, including reduction reactions with Mg metal . While from derivatives with smaller substituents, such as Ph or t Bu, cage compounds are formed upon reduction, derivatives with sterically demanding groups such as Hyp (Si(SiMe 3 ) 3 ) or Ter (2,6‐Mes 2 C 6 H 3 ) are known to form biradicaloid species of the type [P(μ‐NR)] 2 .…”

A Systematic Survey of the Reactivity of Chlorinated N2P2, NP3 and P4 Ring Systems

“…R = tBu), the reduction of N 2 P 2 ring systems leads to the formation of N 4 P 4 cage compounds( left: a-, right: bcage)t hat can be regarded as dimers of the respective biradicals [P(m-NR)] 2 . [59][60][61] Chem.E ur.J.2019, 25,[16311][16312][16313][16314][16315][16316][16317][16318][16319] www.chemeurj.org In our attempts to fully characterize compound 16,i tt ranspired that this speciesw as rather unstablea nd only of intermediaryn ature. Several NMR experiments were runu sing isolated crystals of compound 16 as well as the reaction mixture of 2 and Cp 2 Ti(BTMSA)( Figure S13).…”