- Reactivity studies of group 15 Zintl ions towards homoleptic post-transition metal organometallics: A 'bottom-up' approach to bimetallic molecular clusters
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Reactions between ethylenediamine (en) solutions of the intermetallic Zintl phases K3E7 (E = P, As) and a series of homoleptic post-transition metal organometallics such as Cu5(Mes)5, M(C6H5)2 (M = Zn, Cd) and In(C 6H5)3 have yielded a family of novel bimetallic cluster anions. These new species were isolated as [K(2, 2,2-crypt)] + salts in [K(2,2,2-crypt)]4Cu2E14 (E = P (1), As (2)), [K(2,2,2-crypt)]4ZnE14 (E = P (3), As (4)), [K(2,2,2-crypt)]4CdP14·6py (5) and [K(2,2,2-crypt)]2E7InPh2 (E = P (6), As (7)). Species 2, 3, 5 and 6 were crystallographically characterised by single-crystal X-ray diffraction. The stability of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by 1H, 13C{1H} and 31P{1H} NMR spectroscopy when possible. The Royal Society of Chemistry.
- Knapp, Caroline,Zhou, Binbin,Denning, Mark S.,Rees, Nicholas H.,Goicoechea, Jose M.
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- Oxidation of indium with triphenylbismuth in polar solvents
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The formal-kinetics relationships and products of the reaction of triphenylbismuth with indium in polar solvents were determined. The probable reaction scheme is discussed.
- Maslennikov,Malysheva,Spirina,Klement'eva
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- A phosphine-free, heterogeneous palladium-catalyzed atom-efficient carbonylative cross-coupling of triorganoindiums with aryl halides leading to unsymmetrical ketones
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The first phosphine-free heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl halides with triorganoindiums has been developed that proceeds smoothly under 1 or 2.5 atm of carbon monoxide in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable unsymmetrical ketones with high atom-economy, good yield, and recyclability of the catalyst. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- You, Shengyong,Xiao, Ruian,Liu, Haiyi,Cai, Mingzhong
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p. 13862 - 13870
(2017/11/27)
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- A phosphine-free, atom-efficient cross-coupling of aryl iodides with triarylindiums or trialkynylindiums catalyzed by immobilization of palladium(0) in MCM-41
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The first phosphine-free heterogeneous atom-efficient cross-coupling reaction of aryl iodides with triarylindiums or trialkynylindiums was achieved in THF at 68 °C by using 1 mol% of MCM-41-immobilized palladium(0)-Schiff base complex [MCM-41-N,N-Pd(0)] as catalyst, yielding a variety of unsymmetrical biaryls and arylalkynes in good to excellent yields. The heterogeneous palladium(0) catalyst could easily be prepared via a simple procedure from commercially readily available reagents, and recovered by filtration of the reaction solution and recycled at least 10 times without significant loss of activity.
- Lei, Zhiwei,Liu, Haiyi,Cai, Mingzhong
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- Transition-Metal-Free Cross-Coupling of Indium Organometallics with Chromene and Isochroman Acetals Mediated by BF3·OEt2
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A transition-metal-free coupling of triorganoindium reagents with benzopyranyl acetals mediated by a Lewis acid has been developed. The reaction of R3In with chromene and isochroman acetals in the presence of BF3·OEt2 afforded 2-substituted chromenes and 1-substituted isochromans, respectively, in good yields. The reactions proceed with a variety of triorganoindium reagents (aryl, heteroaryl, alkynyl, alkenyl, alkyl) using only 50 mol % of the organometallic, thus demonstrating the efficiency of these species. Preliminary mechanistic studies indicate the formation of an oxocarbenium ion intermediate in the presence of the Lewis acid.
- Gil-Negrete, José M.,Sestelo, José Pérez,Sarandeses, Luis A.
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p. 4316 - 4319
(2016/10/12)
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- Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: Synthesis and photochemical studies
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The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.
- Mosquera, ngeles,Frnandez, M. Isabel,Lopez, Moiss Canle,Sestelo, Jos Prez,Sarandeses, Luis A.
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p. 14524 - 14530
(2015/01/09)
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- Synthesis of functionalized thiophenes and oligothiophenes by selective and iterative cross-coupling reactions using indium organometallics
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The synthesis of unsymmetrical 2,5-disubstituted thiophenes by selective and sequential palladium-catalyzed cross-coupling reactions of indium organometallics with 2,5-dibromothiophene is reported. Following an iterative coupling sequence, α-oligothiophenes were synthesized in good yields and with high atom economy.
- Montserrat Martinez,Pena-Lopez, Miguel,Sestelo, Jose Perez,Sarandeses, Luis A.
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p. 3892 - 3898
(2012/06/04)
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- Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles
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The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R3In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the correspond
- Perez,Sestelo,Sarandeses
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p. 4155 - 4160
(2007/10/03)
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