The Quest for Mononuclear Gold(II) and Its Potential Role in Photocatalysis and Drug Action

Heinze, Katja

doi:10.1002/anie.201708349

Cited by 32 publications

(22 citation statements)

References 99 publications

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“…6). This work contributes to further advance our knowledge of gold chemistry, which, despite recent advances (12,(52)(53)(54)(55)(56)(57), remains far behind that of the other transition metals in terms of structures and reactivity.…”

Section: Resultsmentioning

confidence: 93%

Evidence for genuine hydrogen bonding in gold(I) complexes

Rigoulet

Massou

Carrizo

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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The ability of gold to act as proton acceptor and participate in hydrogen bonding remains an open question. Here, we report the synthesis and characterization of cationic gold(I) complexes featuring ditopic phosphine-ammonium (P,NH+) ligands. In addition to the presence of short Au∙∙∙H contacts in the solid state, the presence of Au∙∙∙H–N hydrogen bonds was inferred by NMR and IR spectroscopies. The bonding situation was extensively analyzed computationally. All features were consistent with the presence of three-center four-electron attractive interactions combining electrostatic and orbital components. The role of relativistic effects was examined, and the analysis is extended to other recently described gold(I) complexes.

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Section: Resultsmentioning

confidence: 93%

Evidence for genuine hydrogen bonding in gold(I) complexes

Rigoulet

Massou

Carrizo

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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“…However, counter ion and solvent dependent Au III (porph *À )!Au II (porph) valence isomerization equilibria have been observed for porphyrinato gold complexes (porph 2À = substituted porphyrinato(2-)). [53][54][55] Here we combine protic ADCs with redox-active ferrocenyl substituents coordinated to gold(I). We describe the synthesis of protic ferrocenyl ADC gold(I) complexes starting from an isocyanoferrocene gold(I) complex, their solid state structures and their redox properties using cyclic voltammetry, square wave voltammetry, chemical oxidation followed by UV/Vis/NIR and X-band EPR spectroscopy and density functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

2021

Self Cite

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Two mononuclear protic ferrocenyl acyclic diamino carbene gold(I) complexes AuCl[C(NHFc)(NR 2 )] were prepared by nucleophilic attack of diethylamine (R = Et) and diisopropylamine (R = i Pr) at the ferrocenyl substituted isocyanide complex chlorido (isocyanoferrocene)gold(I) AuCl(CNÀ Fc). In the solid state, the multifunctional protic carbene gold(I) complexes display intermolecular aurophilic interactions or intermolecular NH•••Cl hydrogen bonding in addition to intramolecular non-classical NH•••Fe hydrogen bonds. Oxidation of the AuCl[C(NHFc)(NR 2 )] complexes initially takes place at the iron centres giving highly coloured ferrocenium ions, which subsequently likely undergo electron transfer from gold(I) to iron(III) yielding putative EPRactive gold(II) species.

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“…Addition reactions such as that shown in Scheme 1 are efficiently catalyzed primarily by group 9 and 10 metal complexes [e.g., Pd(0), Pt(0), Ni(0), Rh(I)], and in which electronically stable oxidation states of the catalytic metals are generated during the oxidative addition step. Single-site Au(0) would not be anticipated as an active catalyst for this purpose, because not only is Au(II) an unstable oxidation state, 2 but also the oxidation potential of metallic Au is too high. In contrast, Au(I) complexes might formally be expected to be catalytically active as the redox couple Au(I)/Au(III) is isoelectronic to Pd(0)/Pd(II).…”

Section: Introductionmentioning

confidence: 99%

Nanogold(0)-Catalyzed Addition of Heteroelement σ Linkages to Functional Groups

Stratakis

Lykakis

2019

Synthesis

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In recent years, supported Au nanoparticles and nanoporous Au materials have shown remarkable catalytic activity in the activation of σ heteroelement linkages such as, Si–H, Si–Si, B–B and B–Si, and their subsequent addition to functional groups, primarily π bonds. In this review article we discuss the reaction modes known to date, and attempt to discuss the mechanistic clues of these transformations which are rather unexpected in terms of conventional transition-metal catalysis concepts, given that the catalytic sites are metallic Au(0).1 Introduction2 Activation of Hydrosilanes2.1 Reactions of Hydrosilanes with Alkynes2.1.1 Hydrosilylation2.1.2 Dehydrogenative Coupling2.2 Reactions of Hydrosilanes with Allenes2.3 Reactions of Hydrosilanes with Carbonyl Compounds and Imines2.4 Reactions of Hydrosilanes with α-Diazo Carbonyl Compounds2.5 Miscellaneous Transformations from the Nano Au-Catalyzed Activation of Hydrosilanes3 Activation of Disilanes3.1 Disilylation of Alkynes3.2 Reactions of 1,1,2,2-Tetramethyldisilane with Alkynes4 Activation of Diboranes4.1 Diborylation of Alkenes4.2 Diborylation of Alkynes4.3 Diborylation of Allenes4.4 Diborylation of Methylenecyclopropanes5 Activation of Silylboranes5.1 Silaboration of Alkynes5.2 Silaboration of Allenes5.3 Silaboration of Unactivated Epoxides and Oxetanes5.4 Reactions of Silylboranes with Aromatic Carbonyl Compounds6 Conclusions and Future Perspectives

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The Quest for Mononuclear Gold(II) and Its Potential Role in Photocatalysis and Drug Action

Cited by 32 publications

References 99 publications

Evidence for genuine hydrogen bonding in gold(I) complexes

Evidence for genuine hydrogen bonding in gold(I) complexes

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

Nanogold(0)-Catalyzed Addition of Heteroelement σ Linkages to Functional Groups

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