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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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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| _version_ | 1850283634809896960 |
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| author | Detlef Schröder Helmut Schwarz |
| author_facet | Detlef Schröder Helmut Schwarz |
| author_sort | Detlef Schröder |
| collection | DOAJ |
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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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| format | Article |
| id | doaj-art-4803c4c5867641cdb056aed48cc363e2 |
| institution | OA Journals |
| issn | 0009-4293 2673-2424 |
| language | deu |
| publishDate | 1989-10-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj-art-4803c4c5867641cdb056aed48cc363e22025-08-20T01:47:44ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24241989-10-01431010.2533/chimia.1989.317Experimental Determination of Primary and Secondary Deuterium Isotope Effects in the FeI-Mediated CH/CC Bond Activation of [Fe(4-Heptanone)]⊕ Complexes in the Gas PhaseDetlef Schröder0Helmut Schwarz1Institut für Organische Chemie der Technischen Universität Berlin Strasse des 17. Juni 135, D-1000 Berlin 12Institut für Organische Chemie der Technischen Universität Berlin Strasse des 17. Juni 135, D-1000 Berlin 12 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. https://www.chimia.ch/chimia/article/view/9926 |
| spellingShingle | Detlef Schröder Helmut Schwarz 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 CHIMIA |
| title | 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 |
| title_full | 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 |
| title_fullStr | 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 |
| title_full_unstemmed | 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 |
| title_short | 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 |
| title_sort | 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 |
| url | https://www.chimia.ch/chimia/article/view/9926 |
| work_keys_str_mv | AT detlefschroder experimentaldeterminationofprimaryandsecondarydeuteriumisotopeeffectsinthefeimediatedchccbondactivationoffe4heptanonecomplexesinthegasphase AT helmutschwarz experimentaldeterminationofprimaryandsecondarydeuteriumisotopeeffectsinthefeimediatedchccbondactivationoffe4heptanonecomplexesinthegasphase |