Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [Tism<sup>PriBenz</sup>]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Ruccolo, Serge; Rauch, Michael; Parkin, Gerard

doi:10.1039/c7sc00499k

Cited by 26 publications

(7 citation statements)

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“…This type of “inverted ligand field”, in which the occupied antibonding orbitals are localized more on the ligand than the metal, was described previously 67 and more recently observed in a series of metallacarbatrane complexes of copper. 68 The “HOMO inversion” in the [Fe(tpy) 2 ] 2+ complex introduces new ILCT transitions into the visible spectrum, further increases the intensity of transitions in the visible region, and results in an additional shift of the UV-vis spectrum toward lower energies. Similar improvement in the absorption properties due to the presence of new ILCT absorption bands was recently reported for a [Cr(tpy) 2 ] 3+ complex substituted with aryl-based ligands.…”

Section: Discussionmentioning

confidence: 99%

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

Mukherjee

Torres²,

Jakubı́ková

2017

Chem. Sci.

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Section: Discussionmentioning

confidence: 99%

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

Mukherjee

Torres²,

Jakubı́ková

2017

Chem. Sci.

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“…We believe that the present study is barely scratching the surface of s-noninnocence and there are many more cases to be discovered, especially since the presence of inverted ligand fields is now more broadly suspected for transition-metal complexes in the literature. [26] Thee ffects that these bonding scenarios have on transitionmetal-catalyzed reactions can be expected to be of significant relevance.…”

Section: Angewandte Chemiementioning

confidence: 99%

σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal Ni^IV

2019

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Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of −2 at a transition‐metal center. For a series of formal high‐valent NiIV complexes, aryl–CF3 bond‐forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034–8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal NiIV centers are better described as approaching a +II oxidation state, originating from highly covalent metal–ligand bonds, a phenomenon attributable to σ‐noninnocence. A direct consequence is that the elimination of aryl–CF3 products occurs in an essentially redox‐neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of σ‐noninnocence in metal–ligand bonding, and of an essentially redox‐neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.

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“…The case of [Cu(CF 3 ) 4 ] 1– is summarized in an extensive review/concept paper on ligand field inversion by Hoffmann, Alvarez, Mealli, and co-workers . The inverted ligand field concept has since appeared in additional discussions of compounds bearing group 11 elements. − …”

Section: Introductionmentioning

confidence: 99%

The Myth of d⁸ Copper(III)

et al. 2019

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Seventeen Cu complexes with formal oxidation states ranging from Cu I to Cu III are investigated through the use of multiedge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations. Analysis reveals that the metal−ligand bonding in high-valent, formally Cu III species is extremely covalent, resulting in Cu K-edge and L 2,3-edge spectra whose features have energies that complicate physical oxidation state assignment. Covalency analysis of the Cu L 2,3edge data reveals that all formally Cu III species have significantly diminished Cu d-character in their lowest unoccupied molecular orbitals (LUMOs). DFT calculations provide further validation of the orbital composition analysis, and excellent agreement is found between the calculated and experimental results. The finding that Cu has limited capacity to be oxidized necessitates localization of electron hole character on the supporting ligands; consequently, the physical d 8 description for these formally Cu III species is inaccurate. This study provides an alternative explanation for the competence of formally Cu III species in transformations that are traditionally described as metal-centered, 2-electron Cu I /Cu III redox processes.

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Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [Tism^PriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Abstract: The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, [TismPriBenz], has been employed to form carbatrane compounds of both the main group metals and transition metals.

Cited by 26 publications

References 176 publications

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal Ni^IV

The Myth of d⁸ Copper(III)

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Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [TismPriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

Abstract: The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, [TismPriBenz], has been employed to form carbatrane compounds of both the main group metals and transition metals.

Cited by 26 publications

References 176 publications

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal NiIV

The Myth of d8 Copper(III)

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Product

Resources

About

Tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl metal complexes, [Tism^PriBenz]M: a new class of metallacarbatranes, isomerization to a tris(N-heterocyclic carbene) derivative, and evidence for an inverted ligand field

σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal Ni^IV

The Myth of d⁸ Copper(III)