| People | Locations | Statistics |
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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Tizzard, Graham J.
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (8/8 displayed)
- 2024A series of crystallographically characterized linear and branched σ-alkane complexes of rhodium : from propane to 3-methylpentanecitations
- 2023Synthesis and characterization of lead metallated non-peripherally substituted octa-octyl tetrabenzo(aza)porphyrins showing face-to-face columnar stacking in the crystal phase
- 2023Synthesis and characterization of lead metallated non-peripherally substituted octa-octyl tetrabenzo(aza)porphyrins showing face-to-face columnar stacking in the crystal phase
- 2022Aryl, bi-functionalised imidazo[4,5-f]-1,10-phenanthroline ligands and their luminescent rhenium(I) complexescitations
- 2022Aryl, bi-functionalised imidazo[4,5-f]-1,10-phenanthroline ligands and their luminescent rhenium(I) complexescitations
- 2021A Series of Crystallographically Characterized Linear and Branched σ-Alkane Complexes of Rhodium: From Propane to 3-Methylpentanecitations
- 2021A series of crystallographically characterized linear and branched σ-alkane complexes of rhodiumcitations
- 2021A series of crystallographically characterized linear and branched σ-alkane complexes of rhodium:from propane to 3-methylpentanecitations
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article
A series of crystallographically characterized linear and branched σ-alkane complexes of rhodium
Abstract
<p>Using solid-state molecular organometallic (SMOM) techniques, in particular solid/gas single-crystal to single-crystal reactivity, a series of σ-alkane complexes of the general formula [Rh(Cy2PCH2CH2PCy2)(ηn:ηm-alkane)][BArF4] have been prepared (alkane = propane, 2-methylbutane, hexane, 3-methylpentane; ArF = 3,5-(CF3)2C6H3). These new complexes have been characterized using single crystal X-ray diffraction, solid-state NMR spectroscopy and DFT computational techniques and present a variety of Rh(I)···H-C binding motifs at the metal coordination site: 1,2-η2:η2 (2-methylbutane), 1,3-η2:η2 (propane), 2,4-η2:η2 (hexane), and 1,4-η1:η2 (3-methylpentane). For the linear alkanes propane and hexane, some additional Rh(I)···H-C interactions with the geminal C-H bonds are also evident. The stability of these complexes with respect to alkane loss in the solid state varies with the identity of the alkane: from propane that decomposes rapidly at 295 K to 2-methylbutane that is stable and instead undergoes an acceptorless dehydrogenation to form a bound alkene complex. In each case the alkane sits in a binding pocket defined by the {Rh(Cy2PCH2CH2PCy2)}+ fragment and the surrounding array of [BArF4]- anions. For the propane complex, a small alkane binding energy, driven in part by a lack of stabilizing short contacts with the surrounding anions, correlates with the fleeting stability of this species. 2-Methylbutane forms more short contacts within the binding pocket, and as a result the complex is considerably more stable. However, the complex of the larger 3-methylpentane ligand shows lower stability. Empirically, there therefore appears to be an optimal fit between the size and shape of the alkane and overall stability. Such observations are related to guest/host interactions in solution supramolecular chemistry and the holistic role of 1°, 2°, and 3° environments in metalloenzymes.</p>