Reversible, Photoinduced Activation of P₄ by Low‐Coordinate Main Group Compounds

Abstract

Two unique systems based on low-coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element-phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.

Ring Expansions of Nonpolar Polyphosphorus Rings

“…In the 31 P{ 1 H} NMR spectrum, the four signals for 6a are observed at 98.9, 86.5, 69.7, and À17.6 ppm, those for 6b at 128.8, 78.1, 40.9, and À10.3 ppm and the signals for 6c are found at 114. 9,87.7,0.9,Supporting Information).…”

Temperature‐Dependent Electron Shuffle in Molecular Group 13/15 Intermetallic Complexes

“…[18,19] Ragogna et al reported the reversible, photoinduced activation of P 4 by reaction with a Ge II compound. [20] In contrast, the formation of a fully reversible equilibrium between a low-valent main-group metal complex and the corresponding intermetallic complex is without precedent.…”

Revealing Germylene Compounds to Attain Superbasicity with Sigma Donor Substituents: A Density Functional Theory Study

“…[35] It can also participate as al igand in organic reactions, adding to unsaturated substrateso rb eing coordinatedby carbenes. [36][37][38][39][40][41][42] Furthermore, germylene plays an important role in the facile activation of small molecules and functional groups. [43][44][45][46] Germanium compounds are also employed in the semiconductor industry.…”