Synthesis and Characterization of Stable Gold(III) PNP Pincer Complexes

Grajeda, Javier; Nova, Ainara; Balcells, David; Bruch, Quinton J.; Wragg, David S.; Heyn, Richard H.; Miller, Alexander J. M.; Tilset, Mats

doi:10.1002/ejic.201800019

Cited by 7 publications

(6 citation statements)

References 59 publications

(59 reference statements)

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“…Gold(III)-complexing ligands offering a phosphine coordination site along with an additional heteroatomic electron donor Received: September 11, 2020 Published: November 10, 2020 41 II, 42 III, 42 IV, 43,44 V, 41,45,46 VI, 47 VII, 48,49 and VIII. are rare, 51 although the use of P,N ligands for gold(III) have allowed the synthesis of organogold(III) complexes and mechanistic studies. 52,53 The mechanism of catalysis with phosphorus-containing gold(III) complexes remains virtually unexplored.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Gold(III)-complexing ligands offering a phosphine coordination site along with an additional heteroatomic electron donor are rare, although the use of P , N ligands for gold(III) have allowed the synthesis of organogold(III) complexes and mechanistic studies. , The mechanism of catalysis with phosphorus-containing gold(III) complexes remains virtually unexplored. Herein, we assess the structure and reactivity of gold(III) complexes of P , N -donor ligands with solution NMR spectroscopic, X-ray crystallographic, and computational (density functional theory, DFT) techniques.…”

Section: Introductionmentioning

confidence: 99%

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P,N-Chelated Gold(III) Complexes: Structure and Reactivity

et al. 2020

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Gold(III) complexes are versatile catalysts offering a growing number of new synthetic transformations. Our current understanding of the mechanism of homogeneous gold(III) catalysis is, however, limited, with that of phosphorus-containing complexes being hitherto underexplored. The ease of phosphorus oxidation by gold(III) has so far hindered the use of phosphorus ligands in the context of gold(III) catalysis. We present a method for the generation of P , N -chelated gold(III) complexes that circumvents ligand oxidation and offers full counterion control, avoiding the unwanted formation of AuCl 4 – . On the basis of NMR spectroscopic, X-ray crystallographic, and density functional theory analyses, we assess the mechanism of formation of the active catalyst and of gold(III)-mediated styrene cyclopropanation with propargyl ester and intramolecular alkoxycyclization of 1,6-enyne. P , N -chelated gold(III) complexes are demonstrated to be straightforward to generate and be catalytically active in synthetically useful transformations of complex molecules.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

P,N-Chelated Gold(III) Complexes: Structure and Reactivity

et al. 2020

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“…It was shown that most of the d‐block metals may be embedded within the binding pockets of the different pincer scaffolds shown in Scheme and Scheme although there are transition metal that remain to be explored in that context (see Scheme ). It is notably that all the metals that have not yet been coordinated to N ‐heterocyclic PNP pincers, were shown to form alkylamide‐, arylamide‐ or silylamide‐based PNP pincer complexes . It therefore seems likely that for these metals N ‐heterocyclic PNP pincers will also prove to be useful ancillary ligands.…”

Section: Future Directionsmentioning

confidence: 99%

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

2020

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Aminodiphosphines and their monoanionic amido derivatives are among the most widely used tridentate ligands. A good share of these ligands, in particular the ones that are based on a rigid N‐heterocyclic core, is predisposed to coordinate in a meridional fashion. Negatively charged derivatives of these meridionally coordinating N‐heterocyclic ligands satisfy all the criteria for PNP pincer scaffolds. Herein, these ligands and their coordination chemistry is reviewed from the perspective of coordination chemistry. For our discussion, ligands containing a protonated N‐heterocycle (e.g. pyrrole‐ or carbazole‐based PNP scaffolds) are to be distinguished from their counterparts that do not contain such an NH‐functionality (e.g. pyridine‐ or triazine‐based PNP scaffolds). Different synthetic methodologies for the preparation of PNP pincer complexes are presented and shown to often depend on the presence or absence of the aforementioned NH‐proton. The different reactivity patterns of the resulting complexes are sub‐divided into two categories, namely into metal‐centered reactions and reactions that result in a chemical transformation at the metal and the ligand. The latter represent ligand‐cooperative transformations, which often play a key role in catalysis, and are showcased by discussing selected applications in catalysis. It will become evident in this review that this relatively young research field is still emerging and far from reaching maturity. Finally, a brief overview on ligand/metal combinations that have not been explored to date is provided, to stimulate future research on PNP pincers featuring a central N‐heterocycle.

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“…[5] More importantly, they are more prone to thermal-or photo-induced decomposition via reductive elimination which can be prevented using chelating ligands. [6] With monodentate ligands, the best stabilities are achieved with aryls, pyridines, imines, dithiocarbamates. [7] Since the beginning of the 2000's, gold chemistry has witnessed a resurgence of interest from the community of researchers.…”

Section: Introductionmentioning

confidence: 99%

“…Compared to gold(I) complexes, they clusterize to a lesser extent through metallophilic (d 8 –d 8 ) interactions [5] . More importantly, they are more prone to thermal‐ or photo‐ induced decomposition via reductive elimination which can be prevented using chelating ligands [6] . With monodentate ligands, the best stabilities are achieved with aryls, pyridines, imines, dithiocarbamates [7] …”

Section: Introductionmentioning

confidence: 99%

Chiral Gold(III) Complexes: Synthesis, Structure, and Potential Applications

Jouhannet

Dagorne

Blanc

et al. 2021

Chemistry A European J

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Since the beginning of the 2000's, homogeneous gold catalysis has emerged as a powerful tool to promote the cyclization of unsaturated substrates with excellent regioselectivity allowing the synthesis of elaborated organic scaffolds. An important goal to achieve in gold catalysis is the possibility to induce enantioselective transformations by the assistance of chiral complexes. Unfortunately, the linear geometry of coordination for gold usually encountered in complexes at the + 1 oxidation states renders this goal very challenging. In consequence, the interest toward the synthesis of chiral gold(III) complexes is steadily growing. Indeed, the square planar geometry of the gold(III) cation appears more suitable to promote chiral induction. Beside catalysis, gold(III) complexes have also shown promising potential in the field of pharmacology. Herein, syntheses and applications of well-defined gold(III) complexes reported over the last fifteen years are summarized.

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Synthesis and Characterization of Stable Gold(III) PNP Pincer Complexes

Cited by 7 publications

References 59 publications

P,N-Chelated Gold(III) Complexes: Structure and Reactivity

P,N-Chelated Gold(III) Complexes: Structure and Reactivity

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

Chiral Gold(III) Complexes: Synthesis, Structure, and Potential Applications

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