Haberhauer, Gebhard; Gleiter, Rolf; Irngartinger, Hermann; Oeser, Thomas; Rominger, Frank:
Cyclic diynes with tetramethyldisilyl groups in the bridges. Syntheses and properties.
1999
In: Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry, Heft 10, S. 2093 - 2097
Artikel/Aufsatz in Zeitschrift / Fach: Chemie
Titel:
Cyclic diynes with tetramethyldisilyl groups in the bridges. Syntheses and properties.
Autor(in):
Haberhauer, Gebhard im Online-Personal- und -Vorlesungsverzeichnis LSF anzeigen; Gleiter, Rolf; Irngartinger, Hermann; Oeser, Thomas; Rominger, Frank
Erscheinungsjahr:
1999
Erschienen in:
Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry, Heft 10, S. 2093 - 2097
ISSN:

Abstract:

Cyclic diynes with tetramethyldisilyl groups as bridging units were synthesized from a,w-bis(chloromethyl)diynes and 1,2-dichloro-1,1,2,2-tetramethyldisilane with Li in the presence of catalytic amts. of biphenyl. X-ray studies of single crystals of the title compds. reveal a twisted-chair conformation for 1,1,2,2-tetramethyl-1,2-disilacycloundeca-4,9-diyne, 1,1,2,2-tetramethyl-1,2-disilacyclododeca-4,10-diyne, 1,1,2,2-tetramethyl-1,2-disilacyclotrideca-4,11-diyne, and 1,1,2,2,6,6,9,9-octamethyl-1,2,6,9-tetrasilacyclododeca-4,10-diyne, and a twisted half-chair conformation for 1,1,2,2-tetramethyl-1,2-disilacyclodeca-4,8-diyne and 1,1,2,2,6,6,7,7-octamethyl-1,2,6,7-tetrasilacyclodeca-4,8-diyne, whereas 1,1,2,2,6,6,8,8-octamethyl-1,2,6,8-tetrasilacycloundeca-4,9-diyne adopts a twisted-boat conformation in the solid state. The He(I) photoelectron spectra of the title compds. reveal ionization energies between 8.5-10 eV for the ionization processes from the p-orbitals.