Structure, Stability, and Catalytic Activity of Fluorine-Bridged Complexes IPr·GaCl2(μ-F)EFn–1 (EFn– = SbF6–, PF6–, or BF4–)

Bour, Christophe; Monot, Julien; Tang, S. C.; Guillot, Régis; Farjon, Jonathan; Gandon, Vincent

doi:10.1021/om4012054

Cited by 47 publications

(25 citation statements)

References 81 publications

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“…To investigate the redox properties of 1 , its reaction with the single-electron oxidant [NO][BF 4 ] was studied. The reaction proceeded with elimination of NO, fluorine abstraction 21,44 and formation of LGaClF (Supplementary Fig. 32), traces of LGaX 2 (X = F, Cl, Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

et al. 2018

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Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl [L(Cl)Ga]2Sb· 1 and bismuthinyl radicals [L(I)Ga]2Bi· 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of [L(Cl)Ga]2Sb· gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The π-bonding contribution is estimated to 9.56 kcal mol−1 by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant π backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures.

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Section: Resultsmentioning

confidence: 99%

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

et al. 2018

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“…This robust protocol may be used with various aldehydes and substituted 3-cyano-acetyl indoles. Other Lewis acids or Lewis bases such as piperidine, triethylamine, FeCl 3 , and Cu(OTf) 2 (42). 70 In this C(sp 3 )-H functionalization of 2-methylazaarenes, the Lewis acidic In(III) center activates both substrates.…”

Section: Indium(iii) Chloridementioning

confidence: 99%

Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The present contribution highlights the most recent and representative developments on the use of Ga and In species in homogeneous catalysis. Recent studies of various ligand‐supported Ga(III) and In(III) compounds in cyclic esters polymerization catalysis for the production of biodegradable polyester materials are also included. Various organic transformations may now be catalyzed using Ga(III) and In(III) Lewis acids allowing access to a wide range of valuable organic molecules through diverse reaction sequences. The recent use of stable and robust N ‐heterocyclic carbene Ga(III) and In(III) compounds as strong π‐Lewis acid catalysts for various organic reactions is also discussed: such species are certainly promising for the future developments of Ga(III)‐ and In(III)‐mediated reactions. Although Lewis acid‐assisted reactions certainly dominate the field in Ga(III) and In(III) chemistry, discrete low‐valent In(I) species, presently emerging in catalysis, clearly display a distinct reactivity allowing their exploitation both as soft Lewis acids and alkyl‐/allyl‐/arylating agents.

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“…This furnished the desired fluorine-bridged species, which proved kinetically stable with Y = SbF 6 (Scheme C. Bour, V. Gandon Account Syn lett 7, left). 39 The counterion could be removed from the coordination sphere of gallium with nitriles such as 2,4,6-trifluorobenzonitrile (Scheme 7, right). 40…”

Section: Figurementioning

confidence: 99%

“…43 The reaction proceeds very well using the isolated complex [IPr·GaCl 2 ][SbF 6 ] as the catalyst. 39,40 Yet, since it is sensitive to moisture, it is more practical to generate the cationic gallium complex in situ from the bench-stable IPr·GaCl 3 and AgSbF 6 . In this case, an excess of the silver salt is recommended to ensure complete anion exchange.…”

Section: Scheme 9 Indium-catalyzed Polycyclization Of Compound 35mentioning

confidence: 99%

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

Bour

Gandon

2015

Synlett

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Dedicated, with admiration, to K. Peter C. Vollhardt NuH Nu H Nu H or R 3 PAuCl/LA LA = Cu(OTf) 2 , In(OTf) 3 , Bi(OTf) 3 , etc. or (NHC)GaCl 2 + NuH = arene, alkene, β-keto amide, -OH, -NH, etc.Abstract Cationic gold(I) complexes are soft Lewis acids that are able to trigger numerous types of nucleophilic attack onto alkenes, allenes, and alkynes (π-acid catalysis). In this account, we initially summarize the novel methods that we have developed to generate such catalysts by silver-free activation of ligated gold(I) chlorides. The advantages of this approach are the use of lower quantities of gold and the ability to scale-up transformations during which the standard gold/silver catalytic system is rapidly decomposed. In the second part, the synthesis and catalytic activity of original organogallium compounds is described. We have shown that (NHC)GaCl 2 +

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Structure, Stability, and Catalytic Activity of Fluorine-Bridged Complexes IPr·GaCl₂(μ-F)EF_n–1 (EF_n^– = SbF₆^–, PF₆^–, or BF₄^–)

Cited by 47 publications

References 81 publications

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

Gallium and Indium Compounds in Homogeneous Catalysis

New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

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