Theoretical Study of Substituent Effects on Geometric and Spectroscopic Parameters (IR,
13C,
29Si NMR) and Energy Decomposition Analysis of the Bonding in Molybdenum Silylidyne Complexes CpMo(CO)2(≡Si‐para‐C6H4X) |
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Abstract: | In this study, we report the substituent effect on the structures, frontier orbital analysis, and spectroscopic properties (IR , 13C , 29Si NMR ) in the molybdenum silylidyne complexes CpMo (CO )2(≡Si‐para ‐C6H4X ) (X = H, F, Cl, CN , NO2 , Me, OMe , NH2 , NHMe ) using MPW1PW91 quantum chemical calculations. The calculated structural parameters and spectral parameters are compatible with the experimental values in similar complexes. The nature of the chemical bond between the [Cp(OC ) 2Mo ]− and [Si‐para ‐C6H4X ]+ fragments was explored with energy decomposition analysis (EDA ). The percentage composition in terms of the defined groups of frontier orbitals for CpMo (CO )2(≡Si‐para ‐C6H4X ) complexes was investigated to explore the character of the metal–ligand bonds. The linear correlations between the properties and Hammett constants (σ p) were illustrated. Natural bond orbital analysis (NBO ) was used to illustrate the electronic structure of the complexes. |
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Keywords: | Carbyne complexes Substituent effect
13C and
29Si nuclear magnetic resonance chemical shifts Energy decomposition analysis |
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