Ambivalent Lewis Acid/Bases with Symmetry Signatures and Isolobal Analogies

Mingos, D. Michael P.

doi:10.1007/430_2013_120

Cited by 11 publications

(7 citation statements)

References 109 publications

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“…The molecular orbital interaction of SO2 with this MOF was previously studied by Arcís-Castillo et al 13 using DFT calculations and it was reported before by many authors for other metal complexes . [39][40][41][42] The results of our calculations agree with those of Arcís-Castillo et al except for the interpretation: we do not identify the mixing between the hybridized Pt d z 2 -pz orbital 43 and the π * LUMO (lowest unoccupied molecular orbital) of the SO2 as a π-backbonding because of the absence of π symmetry in this interaction . 43 Below we discuss in more detail the molecular orbital interaction between SO2 and the metal center.…”

Section: The So 2 Binding Mechanismsupporting

confidence: 85%

“…Because for a d 8 electron count the d z 2 is doubly occupied, the molecule can act only as an electron acceptor. 42 Since the d z 2 is fully occupied, the molecule orients in such a way to decrease the antibonding σ-type of interaction between the HOMO of the molecule and the Pt d 2 z , thus adopting an η 1 -pyramidal configuration 40 with the angle between the Pt and the molecular plane of the SO2 being θ=101.2 • (PBE+D2). In this bent configuration, the LUMO of the molecule interacts with a polarized molecular orbital of Pt (see Fig.…”

Section: The So 2 Binding Mechanismmentioning

confidence: 99%

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Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

Fernández-Blanco¹,

Piñeiro‐López²,

Jiménez‐Ruiz³

et al. 2022

Preprint

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The adsorption mechanism of SO2 in the Hofmannlike coordination polymer Fe(pz)[Pt(CN)4] is studied using inelastic neutron scattering and density functional theory calculations. We find that the most important spectral change upon gas adsorption is the blueshift of the low energy peak found at 100 cm −1 , a feature that is fully confirmed by the computed neutron-weighted phonon density of states. Our calculations suggest that the origin of this change is twofold: i) an increase in the force constant of the cyanide out-of-plane movement due to the binding of the gas onto the Pt(CN)4 plane, and ii) the hampered rotation of the pyrazine due to steric hindrance. The high energy region of the neutron scattering data whose spectral weight is dominated by the internal vibrations of the pyrazine is negligibly affected by the presence of the gas as expected from a physisorption type of binding.

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Section: The So 2 Binding Mechanismsupporting

confidence: 85%

Section: The So 2 Binding Mechanismmentioning

confidence: 99%

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

Fernández-Blanco¹,

Piñeiro‐López²,

Jiménez‐Ruiz³

et al. 2022

Preprint

View full text Add to dashboard Cite

show abstract

“…The inherent ambiguity in assigning oxidation states in organometallic chemistry surfaced early on, as a reviewer reminded us, in the considerations of the bonding in olefin complexes: are they such or metallacyclopropanes? − The reader is also directed to a thoughtful discussion of donor and acceptor perspectives in inorganic chemistry by Mingos. , We also mention here an interesting resent paper by Goesten and co-workers, on six-coordinated group 13 complexes . They argue convincingly that the bonding in these should be seen as electron-rich hypervalent.…”

Section: Computational Probing Of the Possibility Of Inverting Ligand...mentioning

confidence: 95%

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields

et al. 2016

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We begin with a brief historical review of the development of our understanding of the normal ordering of nd orbitals of a transition metal interacting with ligands, the most common cases being three below two in an octahedral environment, two below three in tetrahedral coordination, and four below one in a square-planar environment. From the molecular orbital construction of these ligand field splittings evolves a strategy for inverting the normal order: the obvious way to achieve this is to raise the ligand levels above the metal d's; that is, make the ligands better Lewis bases. However, things are not so simple, for such metal/ligand level placement may lead to redox processes. For 18-electron octahedral complexes one can create the inverted situation, but it manifests itself in the makeup of valence orbitals (are they mainly on metal or ligands?) rather than energy. One can also see the effect, in small ways, in tetrahedral Zn(II) complexes. We construct several examples of inverted ligand field systems with a hypothetical but not unrealistic AlCH3 ligand and sketch the consequences of inversion on reactivity. Special attention is paid to the square-planar case, exemplified by [Cu(CF3)4](-), in which Snyder had the foresight to see a case of an inverted field, with the empty valence orbital being primarily ligand centered, the dx2-y2 orbital heavily occupied, in what would normally be called a Cu(III) complex. For [Cu(CF3)4](-) we provide theoretical evidence from electron distributions, geometry of the ligands, thermochemistry of molecule formation, and the energetics of abstraction of a CF3 ligand by a base, all consistent with oxidation of the ligands in this molecule. In [Cu(CF3)4](-), and perhaps more complexes on the right side of the transition series than one has imagined, some ligands are σ-noninnocent. Exploration of inverted ligand fields helps us see the continuous, borderless transition from transition metal to main group bonding. We also give voice to a friendly disagreement on oxidation states in these remarkable molecules.

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“…Because for a d 8 electron count the d z 2 is doubly occupied, the molecule can act only as an electron acceptor. 50 Since d z 2 is fully occupied, the molecule orients in such a way to decrease the antibonding σ interaction between the HOMO of the molecule and the Pt d z 2 , thus adopting an η 1 -pyramidal configuration 48 with the angle between Pt and the molecular plane of SO 2 being θ = 101.2°(PBE+D2). In this bent configuration, the LUMO of the molecule interacts with a polarized molecular orbital of Pt (see Figure S6), which is a hybridized Pt d z 2 −p z orbital, the polarized character resulting from the addition (bigger lobe) and cancellation (smaller lobe) of the two d z 2 and p z amplitudes.…”

Section: ■ Introductionmentioning

confidence: 99%

Probing the SO₂Adsorption Mechanism in Hofmann Clathrates via Inelastic Neutron Scattering and Density Functional Theory Calculations

et al. 2022

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The adsorption mechanism of SO2 in the Hofmann-like coordination polymer Fe(pz)[Pt(CN)4] is studied using inelastic neutron scattering and density functional theory calculations. We find that the most important spectral change upon gas adsorption is the blue shift of the low-energy peak found at 100 cm–1, a feature that is fully confirmed by the computed neutron-weighted phonon density of states. Our calculations suggest that the origin of this change is twofold: (i) an increase in the force constant of the cyanide out-of-plane movement due to the binding of the gas onto the Pt(CN)4 plane and (ii) the hampered rotation of the pyrazine due to steric hindrance. The high-energy region of the neutron scattering data whose spectral weight is dominated by the internal vibrations of the pyrazine is negligibly affected by the presence of the gas as expected from a physisorption type of binding.

show abstract

Ambivalent Lewis Acid/Bases with Symmetry Signatures and Isolobal Analogies

Cited by 11 publications

References 109 publications

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields

Probing the SO₂Adsorption Mechanism in Hofmann Clathrates via Inelastic Neutron Scattering and Density Functional Theory Calculations

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Ambivalent Lewis Acid/Bases with Symmetry Signatures and Isolobal Analogies

Cited by 11 publications

References 109 publications

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

Probing the SO$_2$ adsorption mechanism in Hofmann clathrates via inelastic neutron scattering and density functional theory calculations

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields

Probing the SO2Adsorption Mechanism in Hofmann Clathrates via Inelastic Neutron Scattering and Density Functional Theory Calculations

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Probing the SO₂Adsorption Mechanism in Hofmann Clathrates via Inelastic Neutron Scattering and Density Functional Theory Calculations