Enhanced Metallophilicity in Metal–Carbene Systems: Stronger Character of Aurophilic Interactions in Solution

Vellé, Alba; Rodrı́guez-Santiago, Luis; Sodupe, Mariona; Miguel, Pablo J. Sanz

doi:10.1002/chem.201904507

Cited by 13 publications

(4 citation statements)

References 46 publications

(68 reference statements)

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“…Consequently, the calculated BO indexes suggest appreciable metallophilic interactions to be responsible for dimer formation. (Note that the calculated BO values are in good agreement with literature values [ 8 , 45 ]).…”

Section: Resultssupporting

confidence: 89%

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

et al. 2021

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A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

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Section: Resultssupporting

confidence: 89%

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

et al. 2021

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“…[32] The silver cations are separated by 3.818 (1) Å ruling out the presence of metallophilic interactions. [33] For 6, as expected, the two gold(I) cations are also in a linear environment and bound to C-and N-sites from two different ligands. The C−Au−N angles equal to 172.7(4) and 172.7(5)°.…”

Section: Scheme 3: Synthesis Of the Silver(i) And Gold(i) Complexes 3-6supporting

confidence: 59%

Dinuclear silver(I) and gold(I) complexes with chiral oxazoline‐NHC ligands

Hoffmann

Dagorne

Pale

et al. 2022

Journal of Organometallic Chemistry

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“…The interaction energy of the Au I ···Au I interaction is even up to 12 kcal/mol, which is much stronger than van der Waals interactions and comparable with strong hydrogen bonds. Similar strong closed-shell interactions are also found in some other transition metals such as Cu I , Ag I , Hg II , and Au III , which is a phenomenon known as metallophilicity. − …”

Section: Introductionmentioning

confidence: 53%

The Covalent Au^I–Au^I Bond in (AuF)_n (n = 2∼4): A Perspective to Understand the Closed-Shell Au^I···Au^I Interaction

Wang

et al. 2021

Inorg. Chem.

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The nature of closed-shell AuI···AuI attraction is still a conundrum in theoretical chemistry. However, for Au2F2 with a zigzag conformation, the d10–d10 closed-shell interaction between the AuF monomers is demonstrated as a coordinate covalent bond. Chemical bonding analysis reveals that the strong AuI···AuI attraction is caused by the participation of the extraordinary active 5d orbital of Au. Based on our study, one of the 5d orbitals of the Au atom is activated to hybridize with its 6s and 6p orbitals to form hybridized dsp2 orbitals, where each Au atom is both an electron donor (Lewis base) and acceptor (Lewis Acid) in dimerization. Actually, the closed-shell AuI···AuI interaction in the zigzag conformation of Au2X2 (X = F, Cl, Br, I, or NH2) is covalent. Our results provide a rather simple but clear-cut example, where mysterious AuI···AuI attractions can be possibly explained by the covalent bond theory.

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Enhanced Metallophilicity in Metal–Carbene Systems: Stronger Character of Aurophilic Interactions in Solution

Abstract: Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 13 publications

References 46 publications

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Dinuclear silver(I) and gold(I) complexes with chiral oxazoline‐NHC ligands

The Covalent Au^I–Au^I Bond in (AuF)_n (n = 2∼4): A Perspective to Understand the Closed-Shell Au^I···Au^I Interaction

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Enhanced Metallophilicity in Metal–Carbene Systems: Stronger Character of Aurophilic Interactions in Solution

Abstract: Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 13 publications

References 46 publications

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Dinuclear silver(I) and gold(I) complexes with chiral oxazoline‐NHC ligands

The Covalent AuI–AuI Bond in (AuF)n (n = 2∼4): A Perspective to Understand the Closed-Shell AuI···AuI Interaction

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The Covalent Au^I–Au^I Bond in (AuF)_n (n = 2∼4): A Perspective to Understand the Closed-Shell Au^I···Au^I Interaction