Triple the fun: tris(ferrocenyl)arene-based gold(<scp>i</scp>) complexes for redox-switchable catalysis

Straube, Axel; Coburger, Peter; Dütsch, Luis; Hey‐Hawkins, Evamarie

doi:10.1039/d0sc03604h

Cited by 27 publications

(29 citation statements)

References 141 publications

(165 reference statements)

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“…Also silver-free activation by e. g. in situ replacing the chlorido ligand using alkali metal salts, copper(II) triflate or methyl triflate is possible. [36][37][38][39][40] Alternatively, introducing ferrocenyl (Fc) as redox-active moiety in carbene [41][42][43][44] (Scheme 1) or phosphane ligands [45] and oxidizing the ferrocene to ferrocenium can initiate catalysis. The reversible on/off switching of the catalyst leads to redox-switchable gold catalysis.…”

Section: Introductionmentioning

confidence: 99%

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

2021

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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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Section: Introductionmentioning

confidence: 99%

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

2021

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“…Very recently, Hey‐Hawkins et al . also reported tris(ferrocenyl)arene‐based gold(I) complexes for redox‐switchable catalysis on the same substrates, [10v] very elegantly demonstrating that it is possible to access four different oxidation states via sequential oxidation of the ferrocenyl units, and to consequently fine‐tune the catalytic activity of the related gold(I) complex.…”

Section: Introductionmentioning

confidence: 89%

Heteroleptic Dirhodium(II) Complexes with Redox‐Active Ferrocenyl Ligands: Synthesis, Electrochemical Properties, and Redox‐Responsive Chemoselectivity in Carbene C−H Insertion

et al. 2022

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A series of original heteroleptic dirhodium(II) complexes (4 a–j) of formula [Rh2(OAc)3(L)], where L is a redox‐active ferrocenecarboxylate ligand, has been prepared. These dirhodium(II) complexes have been characterised by NMR, mass spectrometry and cyclic voltammetry. All complexes show a quasi‐reversible redox behaviour for the ferrocenyl unit. The latter can be selectively oxidised by [N(4‐C6H4Br)3]+BF4−. Four selected heteroleptic complexes 4 a, 4 b, 4 f and 4 i, have been evaluated as catalysts for the intramolecular decomposition of a diazo compound 5. The ratio between the aromatic substitution product 6 and the aliphatic C−H insertion product 7 increases (up to 19 % increase) when using the in situ generated oxidised form of the dirhodium(II) complexes (4 a+BF4− to 4 i+BF4−). This shows that the oxidation of the ferrocenecarboxylate ligand has an effect on the chemoselectivity of the dirhodium‐catalysed diazo decomposition, and thus that the electronic properties of a complex can be tuned without exchanging ligands.

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“…Hey-Hawkins and coworkers prepared interesting trinuclear gold(I) complexes with C3-symmetric trisphosphanes (Figure 5). [33,34] Although the complexes showed scarce values of activity in the absence of oxidant, complex 48a was finally successful as catalyst in a redox-switchable process, adding different equivalents of 1,1'-diacetylferrocenium tetrakis-(perfluo-tert-butoxy)aluminate [fc'Ac 2 ](TEF) as oxidant to switch on the process, and decamethylferrocene as a reductant to turn off the activity of the active species.…”

Section: Redox-switchable Catalystsmentioning

confidence: 99%

Ferrocenyl Gold Complexes as Efficient Catalysts

2022

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More than half a century after the discovery of the ferrocene structure in 1951, it remains as a suitable building block in many research areas, including catalysis with the development of key chiral catalysts. On the other hand, gold‐mediated catalysis has been raised in recent years, allowing the creation of a great variety of C−C bonds and C‐heteroatom bonds. In this context, this review covers the recent advances made with the combination of these two iconic figures in the organometallic chemistry field, since the first gold catalyzed reaction using a ferrocene ligand reported in 1986. The combination of the excellent properties and versatility of this metallocene, has allowed the obtainment of a plethora of ligands for metal catalysis, although their use joined to gold catalysis is still scarcely explored.

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Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

Abstract: The modular syntheses of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes and their homotrinuclear gold(I) complexes are reported. Choosing the arene core allows to fine-tune the exact oxidation potentials and thus to tailor the...

Cited by 27 publications

References 141 publications

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

Heteroleptic Dirhodium(II) Complexes with Redox‐Active Ferrocenyl Ligands: Synthesis, Electrochemical Properties, and Redox‐Responsive Chemoselectivity in Carbene C−H Insertion

Ferrocenyl Gold Complexes as Efficient Catalysts

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