2000 Alcan Award Lecture - Adventures in organometallic NMR: steric restraints, slowed rotations, and skeletal rearrangements

Authors
Citation
Mj. Mcglinchey, 2000 Alcan Award Lecture - Adventures in organometallic NMR: steric restraints, slowed rotations, and skeletal rearrangements, CAN J CHEM, 79(9), 2001, pp. 1295-1309
Citations number
157
Language
INGLESE
art.tipo
Review
Categorie Soggetti
Chemistry
Journal title
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
ISSN journal
0008-4042 → ACNP
Volume
79
Issue
9
Year of publication
2001
Pages
1295 - 1309
Database
ISI
SICI code
0008-4042(200109)79:9<1295:2AAL-A>2.0.ZU;2-F
Abstract
The structures and NMR fluxionality of a wide variety of organometallic com plexes (including tetrahedral cluster cations and systems of the type (CnRn )ML3, where R = Et, Ph) are discussed. Barriers to tripodal and peripheral substituent rotations are reported, and the relevance of correlated rotatio ns to molecular machines is outlined. Haptotropic shifts in (cyclopenta[def ]phenanthrenyl)MLn and (cyclopenta[l]phenanthrenyl)MLn complexes are ration alized in terms of the aromatic character of the transition states. Likewis e, the barriers to silatropic shifts in polyindenylsilanes can be correlate d with the aromaticity of the intermediate isoindenes. Finally, the use of cobalt clusters to control cyclohexane ring conformations is described.