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...
Saved in:
| Main Author: | |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2010-01-01
|
| Series: | E-Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2010/202161 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832552442325106688 |
|---|---|
| author | Tareq Irshaidat |
| author_facet | Tareq Irshaidat |
| author_sort | Tareq Irshaidat |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-810488b9d80046498594844184edb855 |
| institution | Kabale University |
| issn | 0973-4945 2090-9810 |
| language | English |
| publishDate | 2010-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | E-Journal of Chemistry |
| spelling | doaj-art-810488b9d80046498594844184edb8552025-02-03T05:58:41ZengWileyE-Journal of Chemistry0973-49452090-98102010-01-017243744410.1155/2010/202161A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)]Tareq Irshaidat0Department of Chemistry, College of Sciences, Al-Hussein Bin Talal University, Ma’an, JordanFischer 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.http://dx.doi.org/10.1155/2010/202161 |
| spellingShingle | Tareq Irshaidat A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] E-Journal of Chemistry |
| title | A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] |
| title_full | A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] |
| title_fullStr | A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] |
| title_full_unstemmed | A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] |
| title_short | A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO)4(C(OMe)Me)] |
| title_sort | dft study on selected physical organic aspects of the fischer carbene intermediates m co 4 c ome me |
| url | http://dx.doi.org/10.1155/2010/202161 |
| work_keys_str_mv | AT tareqirshaidat adftstudyonselectedphysicalorganicaspectsofthefischercarbeneintermediatesmco4comeme AT tareqirshaidat dftstudyonselectedphysicalorganicaspectsofthefischercarbeneintermediatesmco4comeme |