Perhalogenated Carba‐<i>closo</i>‐dodecaborate Anions as Ligand Substituents: Applications in Gold Catalysis

Lavallo, Vincent; Wright, James H.; Tham, Fook S.; Quinlivan, Sean

doi:10.1002/anie.201209107

Cited by 141 publications

(69 citation statements)

References 84 publications

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“…As shown in Fig. 5A, using L8 AuNTf 2 as the catalyst, its TONs with phenylacetylene as the substrate reached 8500, a nevertheless pleasing number albeit lower than that (i.e., 22000) achieved by the best catalyst developed by Lavallo (14); however, with 1-dodecyne as the substrate, L8 AuNTf 2 was a much better catalyst than that by Lavallo as its TON reached 3900 while a TON of 435 is reported in the latter case.…”

Section: Discussionmentioning

confidence: 76%

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

Wang

et al. 2014

Nat Commun

142

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Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding.

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Section: Discussionmentioning

confidence: 76%

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

Wang

et al. 2014

Nat Commun

142

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“…Therefore, this unique property of icosahedral carboranes may potentially provide a way for chemists to overcome a fundamental limitation associated with the electronic tunability window and inability to orthogonalize steric and electronic properties of ligands when using classical carbon-based substituents. Furthermore, as was recently shown by Lavallo and co-workers [83], utilization of perhalogenated carborane substituted ligands can drastically improve stability of the corresponding metal-based complexes leading to species with unprecedentedly high catalytic reactivity.…”

Section: Carboranes As Dichotomous Ligand Substituentsmentioning

confidence: 78%

New ligand platforms featuring boron-rich clusters as organomimetic substituents

Spokoyny

2013

Pure and Applied Chemistry

150

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200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the “space race” while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules—a phenomenon best described as “organomimetic”. Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion.

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“…23,24 Complexes of the monocarba-closo-dodecaborate anion with iron, 25 iridium, 26 rhodium, 27−29 and aluminum 30 have been reported, and recently the first cases of catalysis by carborane-gold complexes have been published. 31 In most prior work with metal complexes derived from 1 the attachment to the carborane cage was through the easily functionalized position 1 (the carbon atom). Here, we use attachment in position 12 (the antipodal boron atom), and leave position 1 available for potential further derivatization.…”

Section: ■ Introductionmentioning

confidence: 99%

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

et al. 2016

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The anionic nitriles 1-R-12-NC-CB11H10(-) (R = H, CH3, I, COOH), 12-NC-1-H-CB11Me10(-), and 12-NC-1-H-CB11F10(-) were prepared, and three of them were examined for complex formation with (Et3P)2Pt(II) and (Et3P)2Pd(II). Several stable internally charge-compensated zwitterionic complexes were obtained and characterized. RI-BP86/SV(P) calculations suggest that their dipole moments exceed 20 D. An attempt to measure the dipole moments in solution failed due to insufficient solubility in solvents of low polarity.

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Perhalogenated Carba‐closo‐dodecaborate Anions as Ligand Substituents: Applications in Gold Catalysis

Cited by 141 publications

References 84 publications

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

New ligand platforms featuring boron-rich clusters as organomimetic substituents

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

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Perhalogenated Carba‐closo‐dodecaborate Anions as Ligand Substituents: Applications in Gold Catalysis

Cited by 141 publications

References 84 publications

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

New ligand platforms featuring boron-rich clusters as organomimetic substituents

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB11X11– (X = H, F, CH3) as Ligands on Pt(II) and Pd(II)

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Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)