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Synthesis, Characterization and Catalytic Activity of NHC Gold(I)

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Synthesis, Characterization and Catalytic Activity of NHC Gold(I) Synthesis, Characterization and Catalytic Activity of NHC Gold(I) Polyoxometalate Complexes Fatih Sirindil, Steven Nolan, Samuel Dagorne, Patrick Pale, Aurélien Blanc, Pierre De frémont To cite this version: Fatih Sirindil, Steven Nolan, Samuel Dagorne, Patrick Pale, Aurélien Blanc, et al.. Synthesis, Char- acterization and Catalytic Activity of NHC Gold(I) Polyoxometalate Complexes. Chemistry - A European Journal, Wiley-VCH Verlag, 2018, 24 (48), pp.12630-12637. 10.1002/chem.201801648. hal-02348146 HAL Id: hal-02348146 https://hal.archives-ouvertes.fr/hal-02348146 Submitted on 5 Nov 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Synthesis, Characterization and Catalytic Activity of NHC Gold(I) Polyoxometalate Complexes Fatih Sirindil,[a] Steven P. Nolan,[b]* Samuel Dagorne,[c] Patrick Pale,[a] Aurélien Blanc,[a]* and Pierre de Frémont[c]* [a] Equipe de Synthèse, Réactivité et Catalyse Organométalliques (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France. [b] Department of Chemistry and Center for Sustainable Chemistry, Ghent University, Krijgslaan 281 - S3, 9000 Ghent, Belgium. [c] Laboratoire de Synthèse, Réactivité Organique et Catalyse, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France. RECEIVED DATE Abstract: The new hybrid NHC gold(I) acetonitrile polyoxometalate complexes + + 4- + + 3- {[Au(IPr)(MeCN) ][H ]3[SiW12O40 ] (1), [Au(IPr)(MeCN) ][H ]2[PMo12O40 ] (2), + + 6- + + 3- [Au(IPr)(MeCN) ][H ]5[P2W18O62 ] (3), [Au(IPr)(MeCN) ][H ]2[PW12O40 ] (4), + 3- t + + 3- [Au(IPr)(MeCN) ]3[PMo12O40 ] (5) and [Au(I Bu)(MeCN) ][H ]2[PMo12O40 ] (6)} were readily synthesized in high yield and characterized by NMR and MS-ESI spectroscopy. In a preliminary catalytic study, their activity was assessed under heterogeneous conditions for the ene-yne rearrangement reaction and a cycloisomerization reaction. Additionally, their reactivity and recyclability were tested in the hydration of alkynes under homogeneous conditions. 1 Introduction The gold carbene chemistry has its origins in the early 70’s with the seminal contributions of Minghetti who characterized the first gold-carbene complexes1 and the Lappert group who synthesized a large number of Late Transition Metal complexes supported by Fischer singlet carbenes, including examples bearing N-heterocyclic carbenes (NHC).2 During the 1980’s and 90’s, assumptions were made that because of its noble nature, gold complexes would not be active in homogeneous catalysis. This misconception widely contributed to the underdevelopment of the coordination chemistry of gold. This situation drastically changed in 1998, when Teles described a highly active gold(I)-phosphine complex enabling the hydration of alkynes and triggered a gold rush in homogenous catalysis.3 A second breakthrough in gold catalysis made use of stable free N-heterocyclic carbenes (NHC) discovered by Arduengo.4 These have become popular ligands in organometallic chemistry, especially suitable to provide air/moisture stability to gold complexes.5 Nowadays, organogold chemistry has taken full advantage of the progress achieved in carbene chemistry and various complexes are recognized as outstanding catalysts to activate carbon‒carbon multiple bonds toward intra- or intermolecular nucleophilic additions.6 Oxides of Early Transition Metals such as molybdenum, tantalum, vanadium or tungsten in their highest oxidation states, readily form polyanionic clusters also known as n− polyoxometalates (POMs). They usually belong to the Lindqvist ([M6O19 ]), Anderson n− n− n− [(XM6O24 )], Keggin ([XM12O40 ]) or Dawson ([X2M18O62 ]) types, some of them comprising various isomers (e.g. α, β, γ or ε- isomers of the Keggin structure).7 When X is a hole, the POMs fall into the isopolyanion category. By contrast, when X is a heteroatom (e.g. phosphorus or silicon) generally located at the center of the cluster, the POMs fall into the heteropolyanion category. By similarity to metal organic frameworks (MOFs) organization in the solid state,8 the wide structural diversity of POMs leads to a broad diversity of physical and chemical properties being particularly suitable to design hybrid materials with specific catalytic activities9 and/or supramolecular architectures.10 According to Cronin’s classification11, two classes of hybrid materials are widely available based on covalently bound organic cations (type I) or ionically bound organic cations (type II) with POMs. Ideally, this classification should be extended to take into consideration the emergence of POM hybrid materials comprised of ionically bound cationic 2 organometallic complexes (type III) or covalently bound cationic organometallic complexes (type IV). Reported gold POM compounds made from inorganic gold salts often display limited stability with undesired reduction into gold nanoparticles.12 Recently Nomiya and our group described two series of redox stable gold(I)-phosphine POM hybrid materials (type III) made + 13 2+ 14 with the cationic [Au(PPh3)(MeCN)] fragment or the [{Au(PPh3)}4(μ4-O)] cluster. These species proved to catalyze, under homogeneous or heterogeneous conditions, various nucleophilic additions on C‒C triple bonds (e.g. hydration, hydroarylation and the Meyer- Schuster rearrangement of alkynes).15 In this contribution, we extended the concept of organogold POM hybrid materials by synthesizing and characterizing a series of gold(I)-NHC POM complexes. The initial catalytic activity of these gold complexes was evaluated under heterogeneous conditions in an acetate rearrangement and in the cycloisomerization of N-tosyl 1,6-enyne, then the recyclability of the best catalyst was tested in the hydration of diphenylacetylene. Results and discussion Synthesis of Au(I)-NHC POM complexes. In acetonitrile, the previously reported gold(I) complex [Au(IPr)(OH)] (1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide),16 was reacted with one equivalent of [H4SiW12O40] (silicotungstic acid hydrate), [H3PMo12O40] (phosphomolybdic acid hydrate), [H6P2W18O62] (18-tungsto-2-phosphoric acid hydrate), and [H3PW12O40] (phosphotungstic acid hydrate) to afford the corresponding new gold(I)-NHC complexes + + 4- + + 3- [Au(IPr)(MeCN) ][H ]3[SiW12O40 ] (1), [Au(IPr)(MeCN) ][H ]2[PMo12O40 ] (2), + + 6- + + 3- [Au(IPr)(MeCN) ][H ]5[P2W18O62 ] (3), and [Au(IPr)(MeCN) ][H ]2[PW12O40 ] (4) respectively (Scheme 1). The acid-base reaction is extremely fast, reaching full conversion within 15 minutes at room temperature. The cationic [Au(IPr)(MeCN)]+ fragment, of interest in catalysis, is generated only with water as side-product, without addition of silver(I) salts.17 3 Scheme 1: Formation of gold(I)-NHC POM complexes 1-4. The 1H NMR spectra of 1-4 are very similar to those of the gold(I) hydroxide complex precursor. There is a slight overall downfield shift (comprised between +0.05 and +0.20 ppm) for all signals associated to the NHC moiety. For each spectrum, a broad peak displaying variable + chemical shifts and intensities is associated to residual water and solvated protons [H5O2] from the POMs. The 13C NMR spectra confirm the exclusive formation of the [Au(IPr)(MeCN)]+ fragment, with a characteristic signal around 166.0 ppm.18 There is no trace of [Au(IPr)]+ covalently bound to an oxygen atom from the POM anions.16,19 The 13C NMR spectra of 1-4 are identical and do not provide any insight into the POM structure. The 31P, 29Si and 183W NMR spectra confirm that the POM anions retain their spherical symmetry being unaffected by the presence of the cationic gold fragment.20 (Table 1) Complexes 1-4 are soluble when generated in acetonitrile. However, once they have been dried to afford a powder, their solubility in acetonitrile drastically decreases. They are partially soluble in THF and water, and completely insoluble in alkane, aromatic or chlorinated solvents. Surprisingly, solubility tests of 2 in acetone led to slow decomposition (after a few hours: appearance of a black precipitate of Mo(0), and unaccounted signals visible by 31P NMR spectroscopy). Analyses of 1-4 by mass spectroscopy, in positive mode, revealed the expected signal for the [Au(IPr)(MeCN)]+ fragment (m/z = 626.26). + For 2, a slight trace of [{Au(IPr)}2(μ-Cl)] likely due to contamination during the sample preparation is noticeable (m/z = 1205.46).21 Analyses in negative mode revealed a large predominance of the fully deprotonated form of all POM anions, along with traces of [Au(IPr)]+ fragments linked to POMs (via Au−O bond) which are likely formed during the sample analysis. Interestingly the reaction of 1 equivalent of [H3PMo12O40] with three equivalents of + 3- [Au(IPr)(OH)] provides the complex [Au(IPr)(MeCN) ]3[PMo12O40 ] (5) quantitatively within a few minutes. As expected, saturating the POM anion with three NHC gold fragments increases the solubility of 5 compared to 1-4. 1H and 13C NMR and positive ES-MS spectra confirm the 4 clean formation of the [Au(IPr)(MeCN)]+ fragment. 31P NMR and ES-MS spectra
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