Mono-η6 complexes of chromium(II) and chromium(0). Electron demanding substituents, structural and spectroscopic data comparisons

Jagirdar, Balaji R.; Klabunde, Kenneth J.; Palmer, Roger T.; Radonovich, Lewis J.

doi:10.1016/s0020-1693(96)05241-3

Cited by 4 publications

(4 citation statements)

References 38 publications

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“…Finally, for the case of the C 6 H 4 F 2 complex, the C−F carbons are, on the contrary, moved further away from the Cr center, according to the acceptor nature of the −F substituents. This agrees with what was reported by Jagirdar et al, who observed this slight folding also in p -(C 6 H 4 F 2 )Cr(CO) 2 (SiCl 3 ) 2 and attributed it to the significant negative charge present on the F atoms (−0.305851 e Mulliken charge according to B3LYP for the bare arene) and to the corresponding electron repulsion with the O atoms of the Cr(CO) 3 unit, also due to the large anionic radius of the F center. This would result in a Cr−arene distance larger than that obtained for benzene.…”

Section: Resultssupporting

confidence: 92%

“…In conclusion, (i) all of the DFT-based functionals adopted in this work gave a qualitatively identical description of the (η 6 -arene)Cr(CO) 3 complexes and the way their properties are influenced by changing the arene chemical nature (see Figures and and Figures S5 and S6, Supporting Information). (ii) The comparison with the experimental data, when available, ,,− evidenced the ability of all of the methods to reproduce the geometrical features of the complexes within 0.04 Å. This was true in particular for the BP86 method, that showed the best agreement with the experimental structural values.…”

Section: Resultsmentioning

confidence: 71%

“…The only exception was the C 6 H 4 F 2 complex, which showed very poor agreement at all levels of calculation: the methods were in fact able to correctly reproduce the red shift of CO bands with respect to C 6 H 6 Cr(CO) 3 , but the difference between the calculated and the experimental values was very large (it amounts to 52 cm −1 for Δν̃ CO asymm and to 27 cm −1 for Δν̃ CO totsymm at the B3LYP level). Nevertheless, this difference could be more likely due to the difference between the chemical environments in the calculation (gas phase) and in the experiment (CH 2 Cl 2 solution) than to a lack of the computational methods.…”

Section: Resultsmentioning

confidence: 99%

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Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Vitillo¹,

Groppo²,

Bordiga³

et al. 2009

Inorg. Chem.

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The possibility to modulate Cr(CO)(3) properties by grafting it onto metal-organic framework (MOF) linkers of different natures has been investigated using density functional methods. MOF linkers were modeled using clusters constituted by benzene rings doubly substituted in the para position. The effect of the electron-donor or electron-acceptor nature of benzene substituents on the stability of the (eta(6)-arene)Cr(CO)(3) adduct and on the shift of the CO bands has been considered. Different electron-donor (-NH(2), -CH(3), -OH, -COONa) and electron-acceptor (-F, -COOH, -CN, -CF(3)) substituents have been used and the results compared with the bare benzene. C(6)H(4)(COOZnOH)(2) and C(6)H(4)(Zn(4)O(13)C(6)H(5))(2) clusters have also been adopted as models of the MOF-5 benzene rings. The possibility of modulating the stability and the reactivity of Cr(CO)(3) species by grafting them to MOFs with different organic linkers was verified. In particular, this study indicates that electron-acceptor (e.g., C(6)H(4)(COOH)(2)) substituted MOF linkers facilitate the substitution of CO by incoming molecules, whereas the use of electron-donor ones (e.g., C(6)H(4)(OH)(2)) would improve the stability of the Cr(CO)(3) adduct and the ring acidity. Furthermore, an almost linear dependence of the Cr(CO)(3) binding energies on the calculated structural and vibrational features of the tricarbonyl was found, suggesting that the stability of the Cr(CO)(3) adduct can be inferred experimentally from vibrational and diffraction data. In the end, on the basis of the results obtained, it was possible to successfully explain the experimental shift of the CO IR stretching features of grafted Cr(CO)(3) on the UiO-66, CPO-27-Ni, and MOF-5 aromatic linkers and on the benzene rings of poly(ethylstyrene-co-divinylbenzene). The sign of the Delta nu(CO) shift with respect to C(6)H(6)Cr(CO)(3) has been found to be strongly dependent on higher/lower electron density on the ring.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

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Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Vitillo¹,

Groppo²,

Bordiga³

et al. 2009

Inorg. Chem.

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“…The majority of the reported studies of reactions of silanes with metal complexes involve tertiary silanes and examples are illustrated in Table . − …”

Section: Tertiary Silanesmentioning

confidence: 99%

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

1998

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C2-Bridged sandwich and half-sandwich entities with Ti(IV) and Cr(0) centers

Köcher¹,

Lang²

2002

Journal of Organometallic Chemistry

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Mono-η6 complexes of chromium(II) and chromium(0). Electron demanding substituents, structural and spectroscopic data comparisons

Cited by 4 publications

References 38 publications

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

C2-Bridged sandwich and half-sandwich entities with Ti(IV) and Cr(0) centers

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Mono-η6 complexes of chromium(II) and chromium(0). Electron demanding substituents, structural and spectroscopic data comparisons

Cited by 4 publications

References 38 publications

Stability and Reactivity of Grafted Cr(CO)3Species on MOF Linkers: A Computational Study

Stability and Reactivity of Grafted Cr(CO)3Species on MOF Linkers: A Computational Study

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

C2-Bridged sandwich and half-sandwich entities with Ti(IV) and Cr(0) centers

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Product

Resources

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Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study