Static and Dynamic Stereochemistry of Tris(9-triptycyl)stannane Derivatives

Static and dynamic stereochemistry of several tris(9-triptycyl)stannane derivatives Tp3SnX (X = H, halogens, and alkyl groups) were studied. X-ray crystallography of the bromo and methyl compounds showed that the Sn atom was fundamentally tetrahedral and that the three Tp groups meshed with each oth...

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Published inBulletin of the Chemical Society of Japan Vol. 78; no. 3; pp. 487 - 497
Main Authors Yamamoto, Gaku, Ohta, Shozo, Kaneko, Megumi, Mouri, Kaoru, Ohkuma, Miki, Mikami, Ryo, Uchiyama, Yosuke, Minoura, Mao
Format Journal Article
LanguageEnglish
Published TOKYO The Chemical Society of Japan 01.03.2005
Chemical Soc Japan
Chemical Society of Japan
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
GEARING
CONSEQUENCES
C-13
PARITY RESTRICTION
TRIS(9-TRIPTYCYL)CYCLOPROPENIUM PERCHLORATE
CHLORIDE
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Summary:Static and dynamic stereochemistry of several tris(9-triptycyl)stannane derivatives Tp3SnX (X = H, halogens, and alkyl groups) were studied. X-ray crystallography of the bromo and methyl compounds showed that the Sn atom was fundamentally tetrahedral and that the three Tp groups meshed with each other like bevel gears and formed a near-C3 chiral conformation. The rate constants for enantiomerization of the chiral conformation in solution could be obtained by the lineshape analysis of the aromatic proton signals, even when a direct probe for enantiomerization such as a benzyl group was absent. The energy barrier to enantiomerization decreased as the substituent X became bulkier, suggesting that the ground state is more destabilized than the transition state upon introduction of a bulkier group.
ISSN:0009-2673
1348-0634
DOI:10.1246/bcsj.78.487