ISSN:
0009-2940
Keywords:
Alkynes
;
Photoelectronspectroscopy
;
Electronic structure
;
X-ray investigation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The structures of 6-isopropylidene-1,1-dimethyl-1-silacyclodeca-3,8-diyne (2), 1,6-dimethyl-1,6-disilabicyclo[4.4.4]tetradeca-3,8,12-tryine (4), and 1,1,2,2,3,3-hexamethyl-1,2,3-trisilacyclodeca-4,9-diyne (6) have been investigated by means of X-ray crystallography. In 2 and 6 a chair conformation is adopted in the solid solid state. In 4 the three butyne groups are twisted around the Si—Si axis against one another. The torsion along the triple bond axis (Si-CH2-CH2,/Si) amounts to 29.0(1). The He(I) photoelectron (PE) spectra of 2 and 6 together with those of 1,1-dimethyl-1-silacyclodeca-3,8-diyne (1), 1,1,6,6-tetramethyl-1,6-disilacyclodeca-3,8-diyne (3),1,12,2,3,3-hexamethyl-1,2,3-trisilacycloundeca-4,10-diyne (7) have also been recorded. The PE spectra were interpreted on the basis of results from SCF MO calculations (3-21G*). They reveal a smaller splitting of the π-bands in 1-3 as compared to cyclodeca-1,6-diyne. In the PE spectra of 5-7 we encountered a strong interaction between the silicon chain and the in-plane π-orbitals.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971301216
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