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Hydrosilylation Reactions Catalyzed by Rhenium

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Hydrosilylation Reactions Catalyzed by Rhenium molecules ReviewReview HydrosilylationHydrosilylation ReactionsReactions CatalyzedCatalyzed byby RheniumRhenium DuoDuo WeiWei1,2 1,2,, Ruqaya Ruqaya Buhaibeh Buhaibeh 22, ,Yves Yves Canac Canac 22 andand Jean-Baptiste Jean-Baptiste Sortais Sortais 2,3,*2,3, * 11 Univ.University Rennes, Rennes, CNRS, CNRS, ISCR - ISCR-UMR UMR 6226, 6226, F-35000 35000 Rennes, Rennes, France; France; [email protected] [email protected] 22 LCC-CNRS,LCC-CNRS, Université Université dede Toulouse, Toulouse, UPS, UPS, 31400 31400 Toulouse, Toulouse, France; [email protected] (R.B.); [email protected]@lcc-toulouse.fr (Y.C.) (Y.C.) 33 InstitutInstitut Universitaire Universitaire de de France France 1 1 rue rue Descartes, Descartes, 75231 CEDEX Paris 05, Cedex 75231 Paris,05, France France ** Correspondence:Correspondence: [email protected] [email protected] Abstract:Abstract: Hydrosilylation isis anan important process,process, notnot onlyonly inin thethe siliconsilicon industryindustry toto produceproduce siliconsilicon polymers,polymers, butbut alsoalso in finefine chemistry. InIn this review,review, thethe developmentdevelopment ofof rhenium-basedrhenium-based catalystscatalysts forfor thethe hydrosilylationhydrosilylation of of unsaturated unsaturated bonds bonds in in carbonyl-, carbonyl-, cyano-, cyano-, nitro-, nitro-, carboxylic carboxylic acid acid derivatives derivatives and alkenesand alkenes is summarized. is summarized. Mechanisms Mechanisms of rhenium-catalyzed of rhenium-catalyzed hydrosilylation hydrosilylation are discussed. are discussed. Keywords: rhenium; hydrosilylation;hydrosilylation; unsaturatedunsaturated bonds;bonds; carbonyls;carbonyls; alkenesalkenes 1. Introduction Hydrosilylation is aa veryvery versatileversatile transformationtransformation consistingconsisting of thethe additionaddition ofof aa hydrosilane (H-SiR(H-SiR33) toto anan unsaturatedunsaturated bond.bond. OrganosiliconOrganosilicon compoundscompounds havehave foundfound widespreadwidespread applicationsapplications inin our our daily daily lives lives in silicon-basedin silicon-based materials materials such such as silicon as silicon rub- bers,rubbers, adhesives, adhesives, paper paper release release coating, coating, and and so so forth. forth. In In addition, addition, hydrosilylation hydrosilylation isis anan atom economiceconomic reactionreaction toto accessaccess valuablevaluable organosilaneorganosilane intermediatesintermediates forfor finefine chemicalchemical Citation: Wei, D.; Buhaibeh, R.; synthesissynthesis [[1,2].1,2]. For many years, platinum has been the metalmetal ofof choicechoice forfor designingdesigning Canac, Y.; Sortais, J.-B. Citation: Wei, D.; Buhaibeh, R.; hydrosilylationhydrosilylation catalysts,catalysts, Speier’s, Speier’s, Karstedt’s Karstedt’s or Markor Markó’só’s catalysts catalysts being being the most the repre-most Hydrosilylation Reactions Canac, Y.; Sortais, J.-B.; sentative examples (Figure1). Other noble transition metals, such as rhodium, ruthenium, Catalyzed by Rhenium. Molecules representative examples (Figure 1). Other noble transition metals, such as rhodium, Hydrosilylation Reactions Catalyzed iridium or palladium, have also been used in this transformation [3]. However, the limited 2021, 26, 2598. https://doi.org/ ruthenium, iridium or palladium, have also been used in this transformation [3]. by Rhenium. Molecules 2021, 26, x. 10.3390/molecules26092598 availabilityHowever, the of these limited precious availability transition of metalsthese precious has prompted transition researchers metals tohas explore prompted alter- https://doi.org/10.3390/xxxxx nativesresearchers metals to inexplore the periodic alternatives table, inmetals particular in the first periodic row transition table, in metalsparticular such first as iron,row Academic Editor: Vincent Ritleng cobalttransition and metals nickel [such4–6]. as iron, cobalt and nickel [4–6]. Academic Editor: Vincent Ritleng Received: 17 March 2021 O Received: 17 March 2021 O Si Si Cy Accepted: 15 April 2021 Si Si Si N Accepted: 15 April 2021 H PtCl O Pt Published: 29 April 2021 2 6 Pt Pt Published: 29 April 2021 N O Si Si Si Cy Publisher’s Note: MDPI stays neutral Publisher’s Note: MDPI stays with regard to jurisdictional claims in neutral with regard to jurisdictional Speier's catalyst Karstedt's catalyst Marko's catalyst published maps and institutional affil- claims in published maps and iations. institutional affiliations. FigureFigure 1.1. RepresentativeRepresentative platinum-basedplatinum-based hydrosilylationhydrosilylation catalysts.catalysts. InIn thisthis regard,regard, groupgroup 77 transitiontransition metals,metals, manganesemanganese [[7]7] andand rheniumrhenium [[8],8], werewere notnot anan obviousobvious choicechoice atat firstfirst glance.glance. Indeed,Indeed, rheniumrhenium complexes,complexes, inin particularparticular oxo-rheniumoxo-rhenium Copyright:Copyright: © 2021 2021 by by the the authors. authors. compounds,compounds, havehave been been mainly mainly recognized recognized as efficientas efficient catalysts catalysts in oxidations, in oxidations, such assuch epoxi- as LicenseeLicensee MDPI, MDPI, Basel, Basel, Switzerland. Switzerland. dationepoxidation or oxygen or oxygen atom transfer atom reactionstransfer reactions [9–14]. This [9–14]. is highlighted This is highlighted by organo-rhenium(VII) by organo- ThisThis article is an an open open access access article article trioxide,rhenium(VII) particularly trioxide, methyltrioxorhenium particularly methyltrioxorhenium (MeReO3, abbreviated (MeReO3 as, abbreviated MTO), arguably as MTO), one distributeddistributed under under the the terms terms and and ofarguably the most one versatile of the transitionmost versatile metal transition catalysts knownmetal catalysts to date.Rhenium known to is date. also well-knownRhenium is conditionsconditions ofof the Creative Creative Commons Commons toalso promote well-known olefin metathesisto promote [ 15olefin] or aldehydemetathesis olefinations [15] or aldehyde [16]. In complement,olefinations [16]. the co-In 186/188 AttributionAttribution (CC(CC BY) license (https:// ordinationcomplement, chemistry the coordination of rhenium chemistry was explored of rhenium for thepotential was explored application for the of potentialRe creativecommons.org/licenses/by/(http://creativecommons.org/licenses radioisotopes in nuclear medicine and bio-medical chemistry [17,18]. 4.0/)./by/4.0/). Molecules 2021, 26, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/molecules Molecules 2021, 26, 2598. https://doi.org/10.3390/molecules26092598 https://www.mdpi.com/journal/molecules Molecules 2021, 26, 2598 2 of 15 The application of rhenium derivatives in hydrosilylation [19,20] was not unveiled until 2003 [21,22]. Since the application of the lighter congener of rhenium, namely man- ganese, has been increasing lately in hydrosilylation [23,24], we report here the evolution of rhenium in this catalytic transformation. 2. Hydrosilylation of C=O, C=N, C≡N and NO2 Bonds 2.1. Hydrosilylation of Carbonyl Derivatives The first rhenium-catalyzed hydrosilylation was described in 2003 by Toste et al. (Scheme1a). This seminal contribution represents the first example of a hydrosilylation catalyst with a high-valent metal bearing two terminal oxo ligands, reversing the traditional use of metal-oxo complexes in catalysis. Indeed, the hydrosilylation of aldehydes and ke- tones was promoted by the readily available iododioxo(bistriphenylphosphine)rhenium(V) complex [(PPh3)2Re(O)2I] (C1)[21,22]. The scope of this reaction included aromatic or aliphatic ketones and aldehydes with a good tolerance of functional groups (amino, nitro, halo, ester, cyano, cyclopropyl and alkene groups remained untouched). This air and moisture tolerant reaction provides silyl-protected alcohols in a straightforward reduction- protection protocol as bulky hydrosilanes were used (HSiMe2Ph, HSiEt3, HSiMe2Ph and HSitBuMe2). A detailed mechanism, supported by experimental evidence, was proposed by the same group [21,25] and confirmed by a computational study by Wu et al. in 2006 [26] (Scheme1b). The first step involves the formal [2 + 2] addition of silane to the Re=O bond in C1 to produce metal hydride I-1, which was isolated and characterized by X-ray diffraction. Alkoxy-metal intermediate I-3 is produced by the addition of rhenium hydride Molecules 2021, 26, x to the carbonyl group. Transfer of the silyl group to the alkoxy ligand, formally a3 retroof 15-[2 + 2] reaction, forms the silyl ether product and regenerates the dioxo catalyst C1. SchemeScheme 1. ReI(O)ReI(O)2(PPh2(PPh3)2 (3C1)2 )( C1catalyzed) catalyzed hydrosilylation hydrosilylation of carbonyl of carbonyl compounds compounds with related with related mechanismmechanism studies. studies. (a ()a Scope) Scope of ofthe the reaction; reaction; (b) (Proposedb) Proposed [2 + [22] addition + 2] addition mechanistic mechanistic pathway; pathway; (c) Proposed ionic outer-sphere mechanistic pathway. (c) Proposed ionic outer-sphere mechanistic pathway. However,Intrigued by the the computational work of Toste, studyRoyo et by al. Wei explored [27] showed in 2005 thatthe ca thetalytic ionic activity outer-sphere of a family of oxo-rhenium complexes (C2–C7, Scheme 2) [28]. All these complexes showed mechanistic pathway (Scheme1c) is energetically more favorable than the [2 + 2] addition activity in the reduction of aliphatic and aromatic aldehydes (six examples) and ketones mechanism
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