The Adsorption of Acetylene and Ethylene on Transition Metal Surfaces

Bernardo, Gabriel; Gomes, J.A.N.F.

doi:10.1007/0-306-47667-3_9

“…The unusual η 1 :η 1 coordination mode of the alkyne moiety with each dicopper unit renders the π electron density of the C�C linkage available for engagement in subsequent reactivity and modification, which provides an unexplored platform to investigate the participation of multiple metal atoms in the transfer of acetylide and alkyne groups. In addition, acetylide 6 might serve as a molecular model of adsorbed acetylene on copper surfaces, [30] or as a tetrametallic structural analogue of Reppe's Cu 2 C 2 catalyst. [4,31] Finally, the binding mode enforced by the DPFN ligand strongly influences the electronic properties of the resulting complexes in comparison with previously reported examples.…”

Section: Discussionmentioning

confidence: 99%

Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Ríos,

See,

Handford

et al. 2023

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Reactions of a dicopper(I) tert‐butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) µ‐acetylide/diyne complexes that were characterized by NMR and UV‐Vis spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. These compounds possess an unusual µ4‐η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal‐metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne‐containing clusters.

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“…Thanks to the high sensitivity of the stretching frequency to the hybridized state of the CC bond, it is then possible to determine and testify the hybridization state of the adsorbed molecule experimentally by measuring the vibrational frequency corresponding to the v 2 (CC) stretching mode. In the case of gaseous C 2 H 2 , C 2 H 4 , and C 2 H 6 , which represent the sp, sp 2 , and sp 3 hybridized systems, v (CC) is measured to be 1974, 1623, and 993 cm –1 , respectively. , The related v (CC) for C 2 H 4 adsorption on transition-metal surfaces are shown in Table . ,, …”

Section: The Adsorption and Activation Of H2 And Reactantmentioning

confidence: 99%

“…In the case of gaseous C 2 H 2 , C 2 H 4 , and C 2 H 6 , which represent the sp, sp 2 , and sp 3 hybridized systems, v(CC) is measured to be 1974, 1623, and 993 cm −1 , respectively. 52,55 The related v(CC) for C 2 H 4 adsorption on transition-metal surfaces are shown in Table 1. 52,56,57 The v(CC) of C 2 H 4 is strongly dependent on the species of transition metal on (111) with a vibration wavelength much longer on Pd (111) than that on Pt (111) and Ni (111).…”

Section: Acs Catalysis Pubsacsorg/acscatalysis Reviewmentioning

confidence: 99%

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Geometric and Electronic Effects in Hydrogenation Reactions

Mao

¹

,

Wang

²

,

Luo

³

et al. 2022

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Selective hydrogenation has a long history of being an important reaction process for the preparation of high-value chemicals. The geometric and electronic structures of the catalysts largely determine their basic catalytic performance, including activity, selectivity, and stability. However, the complexity of the components and structures of the catalytic active sites poses a significant challenge to the characterization and the sequential performance attribution. On the basis of summarizing the geometric and electronic structure research in this field, this Review will pay special attention to the adsorption and activation modes of reactants, reaction kinetics, identification and classification of structural sensitivity, methods for geometric and electronic regulation, and distinctive concepts for catalyst design, to enlighten the further development of high-efficiency hydrogenation catalysts.

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Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Ríos,

See,

Handford

et al. 2023

View full text Add to dashboard Cite

Reactions of a dicopper(I) tert‐butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) µ‐acetylide/diyne complexes that were characterized by NMR and UV‐Vis spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. These compounds possess an unusual µ4‐η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal‐metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne‐containing clusters.

show abstract

The Adsorption of Acetylene and Ethylene on Transition Metal Surfaces

Cited by 10 publications

References 69 publications

Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

Geometric and Electronic Effects in Hydrogenation Reactions

Tetracopper σ‐Bound μ‐Acetylide and ‐Diyne Units Stabilized by a Naphthyridine‐based Dinucleating Ligand

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