Synthesis, X-ray, and DFT Study of the Double-Bond Pyramidalization in 1,7,8,9-Tetraphenyl-4,10,10- trimethyl-4-aza-10-silatricyclo[5.2.1.0.2,6]deca-8-ene-3,5-dione and Its Germanium Analogue

Diels−Alder adducts of 1-sila-2,3,4,5-tetraphenyl-1,1-dimethyl-2,4-cyclopentadiene and 1-germa-2,3,4,5-tetraphenyl-1,1-dimethyl-2,4-cyclopentadiene with N-methylmaleimide and maleic anhydride were prepared by high-pressure reactions. Their X-ray structures were determined and compared to literature...

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Bibliographic Details
Published in:Organometallics 2006-01, Vol.25 (1), p.111-117
Main Authors: Margetić, Davor, Murata, Yasujiro, Komatsu, Koichi, Eckert-Maksić, Mirjana
Format: Article
Language:English
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Summary:Diels−Alder adducts of 1-sila-2,3,4,5-tetraphenyl-1,1-dimethyl-2,4-cyclopentadiene and 1-germa-2,3,4,5-tetraphenyl-1,1-dimethyl-2,4-cyclopentadiene with N-methylmaleimide and maleic anhydride were prepared by high-pressure reactions. Their X-ray structures were determined and compared to literature data. In addition, the B3LYP/6-31G* method was used to study their molecular and electronic structure. X-ray analysis revealed that the extent of pyramidalization of the double bond in all studied compounds is small (molecules 1 and 2) or negligible (3). B3LYP/6-31G* calculations were found to overestimate pyramidalization by 5.3−9.4°, presumably due to crystal-packing forces. The effect of phenyl groups on the geometry of the double bond is discussed.
ISSN:0276-7333
1520-6041
DOI:10.1021/om050671b