Synthesis and Reactions of Enantiopure (Neomenthylcyclopentadienyl)iridium(III) Halides with Silver Salts. A Dramatic Steric Effect on the Competition between Inter- and Intramolecular C-H Activation
Reactions of enantiomerically pure (NMCp)M(PMe[sub 3])(Me)X complexes (NMCp = neomenthylcyclopentadientyl; M = Rh, Ir) have revealed that the 16-electron (NMCp)M(PMe[sub 3])(Me)[sup +] intermediates are achiral (planar) at the metal centers on the time average. Generation of the presumed intermediat...
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Published in | Organometallics Vol. 13; no. 7; pp. 2548 - 2550 |
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Main Authors | , |
Format | Journal Article |
Language | English |
Published |
Washington, DC
American Chemical Society
01.07.1994
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Subjects | |
Online Access | Get full text |
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Summary: | Reactions of enantiomerically pure (NMCp)M(PMe[sub 3])(Me)X complexes (NMCp = neomenthylcyclopentadientyl; M = Rh, Ir) have revealed that the 16-electron (NMCp)M(PMe[sub 3])(Me)[sup +] intermediates are achiral (planar) at the metal centers on the time average. Generation of the presumed intermediate (NMCp)Ir(PMe[sub 3]) by photolysis of (NMCp)Ir(PMe[sub 3])(H)[sub 2] in the presence of hydrocarbons results in intermolecular C-H activation. In contrast, the presumed intermediate (NMCp)M(PMe[sup 3])(Me)[sup +] exhibits only intramolecular C-H activation involving the neomenthyl group. One of these cyclometalation products has been structurally characterized. The different outcomes of these two systems are attributed to energy differences in the transition states based on molecular mechanics calculations. 26 refs., 1 fig. |
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Bibliography: | istex:1CC93BB3766C2075E2D2B6CAF8C35147D6FAF982 ark:/67375/TPS-Q0GF34FK-P AC03-76SF00098 |
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om00019a004 |