A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)]
Fischer carbenes are important starting materials for C-C bond formation via coupling reactions between carbene and wide variety of substituted alkenes or alkynes. This DFT study shed light on unique fundamental organic/organometallic aspects for the C(OMe)Me carbene in the free form and in case of...
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| Main Author: | |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley
2010-01-01
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| Series: | E-Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2010/202161 |
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| Summary: | Fischer carbenes are important starting materials for C-C bond formation via coupling reactions between carbene and wide variety of substituted alkenes or alkynes. This DFT study shed light on unique fundamental organic/organometallic aspects for the C(OMe)Me carbene in the free form and in case of bonding with M(CO)4 (M= Cr, Mo, W). The data illustrate that the structures of the title intermediates include a unique structure stabilizing intramolecular M…C-H interaction (agostic interaction). This conclusion was made based on calculated NMR data (for carbon and hydrogen), structural parameters, energy calculations of conformers (C-C conformation), selected IR stretching frequencies (C-O, C-C, and C-H), and atomic charges. The agostic interaction is most efficient in case of chromium and in general is described as an overlap between the σ-bond electron pair of C-H with an empty d-orbital of the metal. These characterized examples are new addition to the orbital interaction theory. |
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| ISSN: | 0973-4945 2090-9810 |