Facile Skeletal Rearrangement of Polycyclic Disilenes with Bicyclo[1.1.1]pentasilanyl Groups. Issue 44 (10th July 2018)

• Record Type: Journal Article
• Authors: Yokouchi, Yuki; Ishida, Shintaro; Iwamoto, Takeaki
• Is Part Of: Chemistry. Volume 24:Issue 44(2018)
• Page Start: 11393
• Page End: 11401
• Publication Date: 2018-07-10
• Subjects: cluster compounds -- disilenes -- oligosilanes -- rearrangement -- silicon; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201801517
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The unexpected formations of fused polycyclic disilenes2 a and ( E ), ( Z )‐3 b by the reduction of the 1, 2‐dibromodisilanes5 a (R=Me) and5 b (R= i Pr) bearing bicyclo[1.1.1]pentasilanyl (BPS) groups is reported. The disilenes2 a and ( E ), ( Z )‐3 b were characterized by a combination of NMR spectroscopy and X‐ray diffraction analysis (XRD). The reduction of5 b in the presence of 2, 3‐dimethyl‐1, 3‐butadiene provided an ene adduct of the disilene1 b bearing BPS groups, which suggested that an initial product of the reduction of5 b was the disilene1 b . Thermal reactions of2 a and ( E ), ( Z )‐3 b afforded the highly strained saturated silicon clusters4 a and4 b . A computational study suggested that the transformation of1 to2, 3, or4 can involve silyldisilene–disilanylsilylene rearrangement reactions and insertion reactions of a silylene into a Si−Si bond. Abstract : Expect the unexpected : Reduction of a 1, 2‐dibromodisilane bearing highly strained bicyclo[1.1.1]pentasilane cages provided a disilene with a rearranged polycyclic silicon skeleton, which underwent further skeletal isomerization to afford a polycyclic oligosilane (see figure).