Experimental Determination of Primary and Secondary Deuterium Isotope Effects in the FeI-Mediated CH/CC Bond Activation of [Fe(4-Heptanone)]⊕ Complexes in the Gas Phase
The gas-phase behaviour of [Fe(4-heptanone)]⊕ is in several aspects quite distinct from that of other Fe⊕ complexes as far as kinetic details of the individual steps of CH/CC bond activation are concerned. From the study of intramolecular kinetic isotope effects the following is concluded: (i) In t...
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| Main Authors: | , |
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| Format: | Article |
| Language: | deu |
| Published: |
Swiss Chemical Society
1989-10-01
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| Series: | CHIMIA |
| Online Access: | https://www.chimia.ch/chimia/article/view/9926 |
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| Summary: | The gas-phase behaviour of [Fe(4-heptanone)]⊕ is in several aspects quite distinct from that of other Fe⊕ complexes as far as kinetic details of the individual steps of CH/CC bond activation are concerned. From the study of intramolecular kinetic isotope effects the following is concluded: (i) In the production of molecular hydrogen, it is the reductive elimination which is subject to a relatively large isotope effect (kH2/kHD = 2.70); in contrast, β-hydrogen transfer is associated with a small one (kH/kD = 1.05). (ii) For ethylene loss, both the β-CC bond cleavage and the olefine detachment are affected by substitution of deuterium for hydrogen (kH/kD = 1.14 and kH/kD = 1.11, respectively). (iii) The rate-initiating step, i. e. insertion of the (complexed) Fe⊕ into a CH bond, is not subject to a discernible isotope effect.
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| ISSN: | 0009-4293 2673-2424 |