How reduced are nucleophilic gold complexes?

Leach, Isaac F.; Sorbelli, Diego; Belpassi, Leonardo; Belanzoni, Paola; Havenith, Remco W. A.; Klein, Johannes E. M. N.

doi:10.1039/d2dt01694j

Cited by 9 publications

(13 citation statements)

References 76 publications

(101 reference statements)

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“…Remarkably, both increases of q M / q Al and q H 1 / q H 2 are almost symmetrical for all the stationary points, indicating the absence of H 2 polarization and further confirming the bimetallic cooperative radical pair stabilization mechanism. Furthermore, the VDD atomic charge evolution along the reaction profiles suggests that, starting from what we expect to be a formal M(0) species in the initial complexes based on previous results on [ t Bu 3 PAuAl(NON)], 46 the oxidation state at M (and Al) remains formally unaltered.…”

Section: Resultssupporting

confidence: 64%

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Sorbelli

Belpassi²,

Belanzoni

2023

Chem. Sci.

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Section: Resultssupporting

confidence: 64%

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Sorbelli

Belpassi²,

Belanzoni

2023

Chem. Sci.

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“…These results can be rationalized on the basis of the radical-like reactivity of the metal (and aluminyl) fragments and metal’s atomic orbitals. As shown in Scheme S1 and Tables S3 and S6 in the SI, the product formation is favored by starting from [ t Bu 3 PM]· (M = Cu, Au) and [Al(NON)] · radical fragments, suggesting a radical-like reactivity of both gold– and copper–aluminyl complexes, also consistent with gold’s valence 5d 10 6s 1 configuration in gold–aluminyl complexes we recently discussed . Upon spin density analysis on the two isolated metal fragments at the geometry they have in TSI syn Cu and TSI syn Au (Figure c,d), clear differences emerge between gold and copper.…”

Section: Resultsmentioning

confidence: 90%

“…As shown in Scheme S1 and Tables S3 and S6 in the SI, the product formation is favored by starting from [ t Bu 3 PM]· (M = Cu, Au) and [Al(NON)] · radical fragments, suggesting a radical-like reactivity of both gold– and copper–aluminyl complexes, also consistent with gold’s valence 5d 10 6s 1 configuration in gold–aluminyl complexes we recently discussed. 52 Upon spin density analysis on the two isolated metal fragments at the geometry they have in TSI syn Cu and TSI syn Au ( Figure 7 c,d), clear differences emerge between gold and copper. The unpaired electron in the radical [ t Bu 3 PCu] · fragment is highly localized on Cu (0.89 e) with only a small delocalization on P (0.10 e).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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In this work, the mechanism of the insertion reaction of 3-hexyne into Cu−Al and Au−Al bonds in M−aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu−Al and Au−Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold−aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu−Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site�usually showing higher efficiency than copper as a "standard" electrophile in alkyne activation�arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold−aluminyl system is responsible for a less nucleophilic Au−Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M−Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.

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“…We can therefore confirm the identification of a quasi‐d 10 configuration for all the investigated formal gold(III) compounds (1 – 5) . This finding is contrasted by e.g., nucleophilic gold complexes, which have effective 5d 10 6s 1 configurations, as identified by comparative EDA at the same level of theory [16g] …”

Section: Resultsmentioning

confidence: 78%

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d¹⁰Configurations in Formal Gold(III) Complexes

et al. 2022

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Several gold + I and + III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal Cu III complex [Cu(CF 3 ) 4 ] 1À , in which the metal center tries to populate its formally unoccupied 3d x2-y2 orbital via σ-bonding, leading to a reduced d 10 Cu I description. However, Au L 3 -edge X-ray absorption spectroscopy reveals excitation into the dorbital of the Au III species is still possible, showing that a genuine d 10 configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the Au I species, relative to their Ag I and Cu I analogues, due to the low-lying 6s orbital. We propose that gold + I and + III complexes form similar bonds with substrates, owing primarily to participation of the 5d x2-y2 or 6s orbital, respectively, in bonding, indicating why Au I and Au III complexes often have similar reactivity.

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How reduced are nucleophilic gold complexes?

Abstract: Nucleophilic formal gold(–i) and gold(i) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations.

Cited by 9 publications

References 76 publications

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d¹⁰Configurations in Formal Gold(III) Complexes

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How reduced are nucleophilic gold complexes?

Abstract: Nucleophilic formal gold(–i) and gold(i) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations.

Cited by 9 publications

References 76 publications

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Radical-like reactivity for dihydrogen activation by coinage metal–aluminyl complexes: computational evidence inspired by experimental main group chemistry

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes

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Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d¹⁰Configurations in Formal Gold(III) Complexes