Coinage metal cyclic trinuclear compounds (CTCs) are an emerging class of metal coordination compounds that are valuable for many fine optoelectronic applications, even though the reactivity dependence by the different bridging ligands remains somewhat unclear. In this work, to furnish some hints to unravel the effect of substituents on the chemistry of Au(I) CTCs made of a specific class of bridging ligand, we have considered two imidazolate Au(I) CTCs and the effect of different substituents on the pyrrolic N atoms relative to classic metal oxidations with I2 or by probing electrophilic additions. Experimental suggestions depict a thin borderline between the addition of MeI to the N-methyl or N-benzyl imidazolyl CTCs, which afford the oxidized CTC in the former and the ring opening of the CTC and the formation of carbene species in the latter. Moreover, the reactions with iodine yield to the oxidation of the metal centers for the former and just of a metal center in the latter, even in molar excess of iodine. The analysis of the bond distances in the X-ray crystal structures of the oxidized highlights that Au(III)-C and Au(III)-N bonds are longer than observed for Au(I)–C and Au(I)–N bonds, as formally not expected for Au(III) centers. Computational studies converge on the attribution of these discrepancies to an additional case of inverted ligand field (ILF), which solves the question with a new interpretation of the Au(I)–ligand bonding in the oxidized CTCs, which furnishes a new interpretation of the Au(I)-ligand bonding in the oxidized CTCs, opening a discussion about addition/oxidation reactions. Finally, the theoretical studies outputs depict energy profiles that are compatible with the experimental results obtained in the reaction of the two CTCs toward the addition of I2, MeI, and HCl.

A reinterpretation of the Imidazolate Au(I) Cyclic Trinuclear Compounds reactivity with iodine and methyl iodide with the perspective of the Inverted Ligand Field Theory

Galassi, R
;
2022-01-01

Abstract

Coinage metal cyclic trinuclear compounds (CTCs) are an emerging class of metal coordination compounds that are valuable for many fine optoelectronic applications, even though the reactivity dependence by the different bridging ligands remains somewhat unclear. In this work, to furnish some hints to unravel the effect of substituents on the chemistry of Au(I) CTCs made of a specific class of bridging ligand, we have considered two imidazolate Au(I) CTCs and the effect of different substituents on the pyrrolic N atoms relative to classic metal oxidations with I2 or by probing electrophilic additions. Experimental suggestions depict a thin borderline between the addition of MeI to the N-methyl or N-benzyl imidazolyl CTCs, which afford the oxidized CTC in the former and the ring opening of the CTC and the formation of carbene species in the latter. Moreover, the reactions with iodine yield to the oxidation of the metal centers for the former and just of a metal center in the latter, even in molar excess of iodine. The analysis of the bond distances in the X-ray crystal structures of the oxidized highlights that Au(III)-C and Au(III)-N bonds are longer than observed for Au(I)–C and Au(I)–N bonds, as formally not expected for Au(III) centers. Computational studies converge on the attribution of these discrepancies to an additional case of inverted ligand field (ILF), which solves the question with a new interpretation of the Au(I)–ligand bonding in the oxidized CTCs, which furnishes a new interpretation of the Au(I)-ligand bonding in the oxidized CTCs, opening a discussion about addition/oxidation reactions. Finally, the theoretical studies outputs depict energy profiles that are compatible with the experimental results obtained in the reaction of the two CTCs toward the addition of I2, MeI, and HCl.
2022
262
File in questo prodotto:
File Dimensione Formato  
Galassi et al., Inorg. Chem. 2022 vol. 61 issue 8 pp. 3527−3539 .pdf

accesso aperto

Tipologia: Versione Editoriale
Licenza: PUBBLICO - Creative Commons
Dimensione 4.42 MB
Formato Adobe PDF
4.42 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11581/461252
Citazioni
  • ???jsp.display-item.citation.pmc??? 2
  • Scopus 7
  • ???jsp.display-item.citation.isi??? 6
social impact