Synthesis of an anionic Au(I) hydroamination precatalyst supported by charged hydrido-carboranyl phosphine ligands

Kleinsasser, Jack F.; Lee, Sarah E.; Lugo, Christopher A.; Tej, Varun; McArthur, Scott G.; Lavallo, Vincent

doi:10.1016/j.poly.2018.09.027

Cited by 6 publications

(3 citation statements)

References 23 publications

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“…However, catalyst Au3 turned out to be less efficient than Au1 . The lower efficiency of the catalyst was rationalized based on its inability to a generate cationic monocoordinated gold(I) complex by dissociating one of the phosphine ligands . It is worth noting that all these catalysts are remarkably efficient without requiring the additional halide abstracting reagents or cocatalysts.…”

Section: Phosphine Ligandsmentioning

confidence: 99%

Ligand-Enabled Sustainable Gold Catalysis

Kumar

Patil

2022

ACS Sustainable Chem. Eng.

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Gold catalysis has emerged as an efficient tool in the field of synthetic organic chemistry. Despite the significant progress, the need for high catalyst loadings has mainly hampered its applicability in large-scale synthesis. Recent research has showcased the importance of ligand engineering to realize gold-catalyzed organic transformations at low catalyst loadings, at milder reactions conditions, and in greener solvents. In this perspective, we summarized the reports that clearly emphasize the crucial role of ligands in achieving the highly efficient gold-catalyzed organic transformations at low catalysts loadings (≤0.1 mol %) with high turnover numbers and turnover frequencies. This perspective also briefly discusses the challenges and future potential for the development of ppm-level gold catalysis.

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Section: Phosphine Ligandsmentioning

confidence: 99%

Ligand-Enabled Sustainable Gold Catalysis

Kumar

Patil

2022

ACS Sustainable Chem. Eng.

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“…66 Since the first works from Lee et al 67 and Yan et al 68 of carborane iridium(III) complexes, many different iridiumcarborane systems have been reported with diverse uses as chemosensors, or for bioimaging, among others. [69][70][71][72][73][74][75][76] Less developed are those metal-carborane systems peripherally bonded to other metal centres such as gold, 77,78 silver, 79 palladium, 80 or copper. 81 While examples of ruthenacarboranes are found in the literature, 82 strikingly there are no trisbidentate Ru(II)-carborane metal complexes reported.…”

Section: Introductionmentioning

confidence: 99%

Ru(ii) and Ir(iii) phenanthroline-based photosensitisers bearingo-carborane: PDT agents with boron carriers for potential BNCT

et al. 2021

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“…Over the last several years, our group has begun to investigate nonclassical applications of closo -carborane anions 1 (Figure ). , In one embodiment of this approach, we covalently attach the anions to ligand frameworks, such as phosphines − and N-heterocyclic carbenes (NHCs). − The carborane anions are used as bulky and charged alkyl or aryl surrogates, and we have demonstrated the utility of such ligands in catalysis. ,,− NHC 2 (Figure ) is technically a dianionic carbenoid because it, and related species, , have been isolated as alkali metal complexes. With respect to NHC 2 , we have reported only a single anionic Au(I) compound 3 and disclosed no reactivity or further synthetic elaboration of this species (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Strongly Coordinating Ligands To Form Weakly Coordinating Yet Functional Organometallic Anions

et al. 2019

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Weakly coordinating anions (WCAs) are generally tailored to act as spectators with little or no function. Here we describe the implementation of strongly coordinating dianionic carboranyl N-heterocyclic carbenes (NHCs) to create organometallic -ate complexes of Au(I) that serve both as WCAs and functional catalysts. These organometallic WCAs can be utilized to form both heterobimetallic (Au(I)−/Ag(I)+; Au(I)−/Ir(I)+) and organometallic/main group ion pairs (Au(I)−/(CPh3 + or SiEt3 +). Because parent unfunctionalized dianionic carboranyl NHC complex 3 is unstable in most solvents when paired with CPh3 +, novel synthesis methodology was devised to create polyhalogenated carboranyl NHCs, which show superior stability toward electrophilic substitution and cyclometalation chemistry. Additionally, the WCAs containing polyhalogenated carboranyl NHCs are among the most active catalysts reported for the hydroamination of alkynes. This investigation has also produced the first examples of a low-coordinate Au(III) center with two cis accessible coordination sites and the first true dianionic carbene. These studies pave the way for the design of functional ion pairs that have the potential to participate in tandem or cooperative small-molecule activation and catalysis.

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Synthesis of an anionic Au(I) hydroamination precatalyst supported by charged hydrido-carboranyl phosphine ligands

Cited by 6 publications

References 23 publications

Ligand-Enabled Sustainable Gold Catalysis

Ligand-Enabled Sustainable Gold Catalysis

Ru(ii) and Ir(iii) phenanthroline-based photosensitisers bearingo-carborane: PDT agents with boron carriers for potential BNCT

Strongly Coordinating Ligands To Form Weakly Coordinating Yet Functional Organometallic Anions

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