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South African Journal of Chemistry

versión On-line ISSN 1996-840X
versión impresa ISSN 0379-4350

S.Afr.j.chem. (Online) vol.64  Durban  2011




Simulating the agostic interaction in electron-deficient (16-e) group (VI) ML6 complexes: [M(CO)5(C(Me)OMe)] (2+) (M = Cr, Mo, and W) as models



Tareq Irshaidat*

Department of Chemistry, Al-Hussein Bin Talal University, Ma'an, Jordan




A large number of theoretical studies have focused on understanding the molecular features of the agostic interaction in various kinds of molecular environments. However, there is a lack of electronic structure information about the agostic interaction in electron-deficient group (VI) ML6 organometallic complexes. In this simulation study, a unique case of an intramolecular stabilizing interaction has been discovered and evaluated. A geometric analysis revealed that beta-(C-H) and alpha-(C-C) can occupy the seventh and eighth coordination sites in the title Fischer carbene complexes as agostic interactions, which allows classifying the carbene as a η3 ligand in these cases. This theory was supported by the relative energies of the conformers and an NBO analysis. Both C2-C1 (σ) and C2-H1 (σ) were found to interact with the antibonding orbital of M-C6 (σ*), therefore these interactions are classified as σ→σ*. These two simultaneous interactions have significant impact on the carbene characteristics; the structure, the atomic charges, infrared stretching vibrations (C-H, C-C, and C-O), and the 1H and the 13C-NMR chemical shifts. From a fundamental organic-organometallic chemistry point of view, this is a new addition to the orbital interaction theory and to group (VI) chemistry.

Keywords: DFT, agostic interaction, NBO analysis, NPA charges, IR, GIAO-NMR



Full text available only in pdf format.



Some calculations were performed using the computational chemistry facilities at New Mexico State University, USA, special thanks are due to Dr Haobin Wang. We thank Al-Hussein Bin Talal University for support through the research grant 2008/78.



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Received 30 September 2010
Revised 24 October 2010
Accepted 13 December 2010



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