Synthesis and crystal structure of decamethyl-1,4-diphospha-2,3,5,6,7-pentasilabicyclo[2.2.1]heptane and crystal structure of dodecamethyl-1,4-diphospha-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane

Silicon–Phosphorus and Silicon–Arsenic Cage Compounds with Bicyclo[2.2.1]heptane, Bicyclo[3.2.1]octane and Tricyclo[3.3.3.1.03,7]nonane Backbones

“…A n→σ* interaction was shown by NBO ab initio calculations and photoelectron spectra of dodecamethyl‐2,3,5,6,7,8‐hexasila‐1,4‐diphosphabicyclo[2.2.2]octane to be responsible for these interactions. X‐ray analysis of the molecular structure confirmed the increased Si–Si bond length in the cage, which is reported as 235.9 and 236.3 pm 3,4. Normal Si–Si bond lengths are 232–234 pm.…”

“…Previously, we have reported on the synthesis and molecular structure of decamethyl‐2,3,5,6,7‐pentasila‐1,4‐dibismuthabicyclo[2.2.1]heptane from Na 3 Bi/K 3 Bi and dichlorodimethylsilane,5 which decomposes quickly at room temperature forming metallic bismuth. We also reported the synthesis and structure of decamethyl‐2,3,5,6,7‐pentasila‐1,4‐diphosphabicyclo[2.2.1]heptane from Na 3 P/K 3 P and 1,2‐dichlorotetramethyldisilane 4. These syntheses show that in the reactions between sodium/potassium pnictides and halogenated mono‐ and oligosilanes, Si–Si bonds are not only cleaved, but new bonds are formed depending on the reaction conditions.…”

Metalation and Oxidative Coupling of the Unique Cyclic Silylphosphanes (iPr2Si)3PH and (iPr2Si)4PH

“…Five‐membered ring systems, including silicon and phosphorus only are still rare 9. Known species with a Si 4 P backbone are (Me 2 Si) 4 PPh and (Ph 2 Si) 4 PPh, but to the best of our knowledge no structural data are available 10.…”