Polyphenylbiphenyls and polyphenylfluorenes

被引:46
作者
Tong, L [1 ]
Lau, H [1 ]
Ho, DM [1 ]
Pascal, RA [1 ]
机构
[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
关键词
D O I
10.1021/ja980322r
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of highly congested polyphenylbiphenyls and polyarylfluorenes has been prepared and their X-ray structures determined, Decaphenylbiphenyl adopts a very unusual C-1-symmetric geometry (rather than the more intuitive D-2 geometry) in which one of the central benzene rings is distorted into a boat conformation. AM1 calculations confirm that the C-1 geometry is the ground state but indicate that less highly substituted biphenyls should adopt D-2 geometries, The structure of 2,2',4,4',6,6'-hexaphenylbiphenyl supports the latter prediction; this material has crystallographic C-2 symmetry and (except for the orientation of the para phenyl groups) approximate D-2 symmetry in the solid state. Octaphenylfluorenone has been prepared in four steps from tetraphenylcyclopentadienone, Its X-ray structure shows the fluorenone core to be twisted and sterically shielded by the eight peripheral phenyl groups; nevertheless, phenylmagnesium bromide adds easily to the carbonyl group of its equally hindered dimethyl derivative, 2,3,5,6,7,8-hexaphenyl-1,4-di(p-tolyl)fluorenone, Reduction of the resulting fluorenol with TiCl3 gives a nonaarylfluorene, 2,3,5,6,7,8,9-heptaphenyl-1,4-di(p-tolyl)fluorene, and its X-ray structure shows distortions similar to those of octaphenylfluorenone.
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页码:6000 / 6006
页数:7
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