Homogeneous catalysis; Ligand effects; Microwave synthesis; Radical reactions; Reaction mechanisms; Benzoic acid; Catalysis; Catalysts; Chelation; Electronic structure; Esters; Free radical reactions; Nuclear magnetic resonance; Phosphorus compounds; Reaction kinetics; Styrene; X ray crystallography; Atom transfer radical addition; Diphosphine ligand; Dithiocarbamates; Latent initiators; Ligands effect; Quantitative yields; Reaction mechanism; Ligands
Abstract :
[en] Nine representative [Ru(S2CNEt2)2(diphos)] complexes were prepared in almost quantitative yields (91–97%) from [RuCl2(p-cymene)]2, sodium diethyldithiocarbamate trihydrate, and a diphosphine (dppm, dppe, dppp, dppb, dpppe, dppen, dppbz, dppf, or DPEphos), using a novel, straightforward, one-pot procedure. The recourse to a monomodal microwave reactor was instrumental in reaching the thermodynamic equilibria favoring the targeted monometallic trichelates. All the products were fully characterized by using various analytical techniques and the molecular structures of seven of them were determined by X-ray crystallography. NMR, XRD, and IR spectroscopies evidenced a significant contribution of the thioureide resonance form Et2N+=CS22– to the electronic structure of the 1,1-dithiolate ligand. MS/MS spectrometry showed the formation of phosphine-free [Ru(S2CNEt2)2]+ cations in the gas phase, except when starting from [Ru(S2CNEt2)2(dppbz)]. The activity of the nine complexes was probed in three different catalytic processes, viz., the cyclopropanation of styrene with ethyl diazoacetate, the synthesis of vinyl esters from benzoic acid and 1-hexyne, and the atom transfer radical addition (ATRA) of carbon tetrachloride and methyl methacrylate. In the first two reactions, the saturated trichelates were poorly efficient. This was most likely due to their high stability, which prevented the formation of coordinatively unsaturated species. Contrastingly, with a turnover number of 2000 and an initial turnover frequency of 2080 h–1 for a 0.05 mol% catalyst loading, the [Ru(S2CNEt2)2(dppm)] complex emerged as a very robust, latent ATRA initiator, whose activity matched or outperformed those displayed by the most efficient ruthenium catalysts described so far.
Zaragoza, Guillermo; Unidade de Difracción de Raios X, RIAIDT, Universidade de Santiago de Compostela, Campus Vida, Santiago de Compostela, 15782, Spain
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Language :
English
Title :
Synthesis of ruthenium–dithiocarbamate chelates bearing diphosphine ligands and their use as latent initiators for atom transfer radical additions
Publication date :
2021
Journal title :
Journal of Organometallic Chemistry
ISSN :
0022-328X
Publisher :
Elsevier B.V.
Volume :
950
Pages :
121993
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
Delaude, L., Sauvage, X., Demonceau, A., Wouters, J., Synthesis and catalytic evaluation of ruthenium–arene complexes generated using imidazol(in)ium-2-carboxylates and -dithiocarboxylates. Organometallics 28 (2009), 4056–4064, 10.1021/om9002363.
Delaude, L., Betaine adducts of N-heterocyclic carbenes: synthesis, properties, and reactivity. Eur. J. Inorg. Chem., 2009, 1681–1699, 10.1002/ejic.200801227.
Beltrán, T.F., Delaude, L., Recent advances in small clusters and polymetallic assemblies based on transition metals and dithiocarboxylate zwitterions derived from N-heterocyclic carbenes. J. Clust. Sci. 28 (2017), 667–678, 10.1007/s10876-017-1174-4.
Delaude, L., Demonceau, A., Wouters, J., Assessing the potentials of zwitterionic NHC·CS2 adducts for probing the stereoelectronic parameters of N-heterocyclic carbenes. Eur. J. Inorg. Chem., 2009, 1882–1891, 10.1002/ejic.200801110.
Mazars, F., Hrubaru, M., Tumanov, N., Wouters, J., Delaude, L., Synthesis of azolium-2-dithiocarboxylate zwitterions under mild, aerobic conditions. Eur. J. Org. Chem., 2021, 2025–2033, 10.1002/ejoc.202100274.
Champion, M.J.D., Solanki, R., Delaude, L., White, A.J.P., Wilton-Ely, J.D.E.T., Synthesis and catalytic application of palladium imidazol(in)ium-2-dithiocarboxylate complexes. Dalton Trans. 41 (2012), 12386–12394, 10.1039/c2dt31413d.
Naeem, S., Delaude, L., White, A.J.P., Wilton-Ely, J.D.E.T., The use of imidazolium-2-dithiocarboxylates in the formation of gold(I) complexes and gold nanoparticles. Inorg. Chem. 49 (2010), 1784–1793, 10.1021/ic9021504.
Neuba, A., Ortmeyer, J., Konieczna, D.D., Weigel, G., Flörke, U., Henkel, G., Wilhelm, R., Synthesis of new copper(I) based linear 1-D-coordination polymers with neutral imidazolinium-dithiocarboxylate ligands. RSC Adv. 5 (2015), 9217–9220, 10.1039/c4ra09033k.
Ortmeyer, J., Flörke, U., Wilhelm, R., Henkel, G., Neuba, A., A sophisticated approach towards a new class of copper(I) sulfur cluster complexes with imidazolinium-dithiocarboxylate ligands. Eur. J. Inorg. Chem., 2017, 3191–3197, 10.1002/ejic.201700328.
Rungthanaphatsophon, P., Gremillion, A.J., Wang, Y., Kelley, S.P., Robinson, G.H., Walensky, J.R., Structure of copper(I) and silver(I) complexes with zwitterionic ligands derived from N-heterocyclic carbenes. Inorg. Chim. Acta, 514, 2021, 120033, 10.1016/j.ica.2020.120033.
Coucouvanis, D., The chemistry of the dithioacid and 1,1-dithiolate complexes. Lippard, S.J., (eds.) Progress in Inorganic Chemistry, 1970, John Wiley & Sons, Hoboken, NJ, 233–371, 10.1002/9780470166123.ch4.
Eisenberg, R., Structural systematics of 1,1- and 1,2-dithiolato chelates. S.J. Lippard, (eds.) Progress in Inorganic Chemistry, 1970, John Wiley & Sons, Hoboken, NJ, 295–369, 10.1002/9780470166130.ch4.
1968–1977Coucouvanis, D., The chemistry of the dithioacid and 1, 1-dithiolate complexes. Lippard, S.J., (eds.) Progress in Inorganic Chemistry, 1979, John Wiley & Sons, Hoboken, NJ, 301–469, 10.1002/9780470166277.ch5.
Burns, R.P., McCullough, F.P., McAuliffe, C.A., 1, 1-Dithiolato complexes of the transition elements. Emeléus, H.J., Sharpe, A.G., (eds.) Advances in Inorganic Chemistry and Radiochemistry, 1980, Academic Press, New York, NY, 211–280, 10.1016/S0065-2792(08)60094-1 doi:10.1016/S0065-2792(08)60094-1.
Wang, Z.-Q., Lu, S.-W., Guo, H.-F., Hu, N.-H., Synthesis, properties and molecular structure of five-coordinate N,N-dibenzyldithiocarbamate complexes of titanocene, zirconocene and hafnocene. Polyhedron 11 (1992), 1131–1135, 10.1016/S0277-5387(00)84485-X.
Srivastava, A., Ma, Y.-A., Pankayatselvan, R., Dinges, W., Nicholas, K.M., Molybdenum-catalysed allylic amination. J. Chem. Soc., Chem. Commun., 1992, 853–854, 10.1039/c39920000853.
Santos, K., Dinelli, L.R., Bogado, A.L., Ramos, L.A., Cavalheiro, É.T., Ellena, J., Castellano, E.E., Batista, A.A., Crystal structure and catalytic activity of ruthenium (II)/dithiocarbamate complexes in the epoxidation of cyclooctene. Inorg. Chim. Acta 429 (2015), 237–242, 10.1016/j.ica.2015.02.014.
Bond, A.M., Martin, R.L., Electrochemistry and redox behaviour of transition metal dithiocarbamates. Coord. Chem. Rev. 54 (1984), 23–98, 10.1016/0010-8545(84)85017-1.
Zain Aldin, M., Maho, A., Zaragoza, G., Demonceau, A., Delaude, L., Synthesis, characterization, and catalytic evaluation of ruthenium–diphosphine complexes bearing xanthate ligands. Dalton Trans. 47 (2018), 13926–13938, 10.1039/c8dt02838a.
Dragutan, V., Dragutan, I., Delaude, L., Demonceau, A., NHC–Ru complexes—friendly catalytic tools for manifold chemical transformations. Coord. Chem. Rev. 251 (2007), 765–794, 10.1016/j.ccr.2006.09.002.
Delaude, L., Demonceau, A., Retracing the evolution of monometallic ruthenium-arene catalysts for C–C bond formation. Dalton Trans. 41 (2012), 9257–9268, 10.1039/c2dt30293d.
Bennett, M.A., Smith, A.K., Arene ruthenium(II) complexes formed by dehydrogenation of cyclohexadienes with ruthenium(III) trichloride. J. Chem. Soc., Dalton Trans., 1974, 233–241, 10.1039/dt9740000233 Dalton Trans.
Bruker, APEX3, Madison, WI, USA, 2005.
Clark, R.C., Reid, J.S., The analytical calculation of absorption in multifaceted crystals. Acta Crystallogr. Sect. A 51 (1995), 887–897, 10.1107/s0108767395007367.
Sheldrick, G., SHELXT - Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A 71 (2015), 3–8, 10.1107/s2053273314026370.
Sheldrick, G., Crystal structure refinement with SHELXL. Acta Crystallogr. Sect. C 71 (2015), 3–8, 10.1107/s2053229614024218.
Sheldrick, G.M., SADABS, Programs for Scaling and Correction of Area Detection Data. 1996, University of Göttingen, Göttingen, Germany.
Guttiérez Alonso, A., Ballester Reventós, L., Cyclopentadienylruthenium complexes with sulphur donor ligands: II. A comparative study of the reactivity of Ru(η-RC5H4)Cl(L)2 (R = H, CH3, CH3CO; L = CO, Ph2PCH2CH2PPh2/2, P(CH2CH2CN)3) towards anionic (S–S) donor ligands. J. Organomet. Chem. 338 (1988), 249–254, 10.1016/0022-328X(88)80509-6.
Ng, S.Y., Tan, J., Fan, W.Y., Leong, W.K., Goh, L.Y., Webster, R.D., Synthetic, X-ray diffraction, electrochemical, and density functional theoretical studies of (indenyl)ruthenium complexes containing dithiolate ligands. Eur. J. Inorg. Chem., 2007, 3827–3840, 10.1002/ejic.200700070.
Lu, X.L., Vittal, J.J., Tiekink, E.R.T., Tan, G.K., Kuan, S.L., Goh, L.Y., Hor, T.S.A., Comparative reactivity studies of dppf-containing CpRuII and (C6Me6)RuII complexes towards different donor ligands (dppf = 1,1′-bis(diphenylphosphino)ferrocene). J. Organomet. Chem. 689 (2004), 1978–1990, 10.1016/j.jorganchem.2004.03.022.
Pinheiro, S.O., de Sousa, J.R., Santiago, M.O., Carvalho, I.M.M., Silva, A.L.R., Batista, A.A., Castellano, E.E., Ellena, J., Moreira, Í.S., Diógenes, I.C.N., Synthesis, characterization and structure of ruthenium(II) phosphine complexes with N-heterocyclic thiolate ligands. Inorg. Chim. Acta 359 (2006), 391–400, 10.1016/j.ica.2005.05.042.
Ballester, L., Esteban, O., Gutierrez, A., Felisa Perpiñan, M., Ruiz-Valero, C., Gutierrez-Puebla, E., Jesus Gonzalez, M., Reactivity of ruthenium complexes with uninegative (X,S)-donor ligands (X = S,P)—II. Phosphine substitution in [Ru(S,S)2(PR3)2] derivatives. Crystal structure of trans-bis(O-ethyldithiocarbonate)bis(dimethylphenylphosphine)-ruthenium(II). Polyhedron 11 (1992), 3173–3182, 10.1016/S0277-5387(00)83660-8.
Lu, X.L., Ng, S.Y., Vittal, J.J., Tan, G.K., Goh, L.Y., Hor, T.S.A., Structural dynamics and ligand mobility in carboxylate and dithiocarbamate complexes of Ru(II) containing 1,1′-bis(diphenylphosphino)ferrocene (dppf). J. Organomet. Chem. 688 (2003), 100–111, 10.1016/j.jorganchem.2003.08.037.
Hendrickson, A.R., Hope, J.M., Martin, R.L., Tris- and pentakis-dialkyldithiocarbamates of ruthenium, [Ru(S2CNR2)3]n and [Ru2(S2CNR2)5]n (n = +1, 0, –1): chemical and electrochemical interrelations. J. Chem. Soc. Dalton Trans., 1976, 2032–2039, 10.1039/dt9760002032.
Wheeler, S.H., Mattson, B.M., Miessler, G.L., Pignolet, L.H., Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV). Inorg. Chem. 17 (1978), 340–350, 10.1021/ic50180a034.
Jensen, S.B., Rodger, S.J., Spicer, M.D., Facile preparation of η6-p-cymene ruthenium diphosphine complexes. Crystal structure of [(η6-p-cymene)Ru(dppf)Cl]PF6. J. Organomet. Chem. 556 (1998), 151–158, 10.1016/S0022-328X(97)00776-6.
Kühl, O., Phosphorus-31 NMR Spectroscopy. A Concise Introduction for the Synthetic Organic and Organometallic Chemist. 2008, Springer, Berlin, 10.1007/978-3-540-79118-8.
Preti, C., Tosi, G., Zannini, P., Synthesis and characterization of ruthenium dithiocarbamate complexes. J. Inorg. Nucl. Chem. 41 (1979), 485–488, 10.1016/0022-1902(79)80431-5.
Edwards, H.G.M., Lewis, I.R., Turner, P.H., Raman and infrared spectroscopic studies of tris triphenyl phosphine chloride complexes of transition metals. Inorg. Chim. Acta 216 (1994), 191–199, 10.1016/0020-1693(93)03713-K.
Allen, F.H., Watson, D.G., Brammer, L., Orpen, A.G., Taylor, R., Typical interatomic distances: organic compounds. Prince, E., (eds.) International Tables for Crystallography, 2006, Springer, Berlin, 790–811, 10.1107/97809553602060000621.
Chatt, J., Duncanson, L.A., Venanzi, L.M., Electronic structures of dithiocarbamates and xanthates. Nature 177 (1956), 1042–1043, 10.1038/1771042b0.
Quebatte, L., Solari, E., Scopelliti, R., Severin, K., A bimetallic ruthenium ethylene complex as a catalyst precursor for the Kharasch reaction. Organometallics 24 (2005), 1404–1406, 10.1021/om050027x.
Tutusaus, O., Viñas, C., Núñez, R., Teixidor, F., Demonceau, A., Delfosse, S., Noels, A.F., Mata, I., Molins, E., The modulating possibilities of dicarbollide clusters: optimizing the Kharasch catalysts. J. Am. Chem. Soc. 125 (2003), 11830–11831, 10.1021/ja036342x.
Tutusaus, O., Delfosse, S., Demonceau, A., Noels, A.F., Viñas, C., Teixidor, F., Kharasch addition catalysed by half-sandwich ruthenium complexes. Enhanced activity of ruthenacarboranes. Tetrahedron Lett. 44 (2003), 8421–8425, 10.1016/j.tetlet.2003.09.100.
Matyjaszewski, K., From atom transfer radical addition to atom transfer radical polymerization. Curr. Org. Chem. 6 (2002), 67–82, 10.2174/1385272023374445.
Pintauer, T., Matyjaszewski, K., Atom transfer radical addition and polymerization reactions catalyzed by ppm amounts of copper complexes. Chem. Soc. Rev. 37 (2008), 1087–1097, 10.1039/b714578k.
Pintauer, T., Catalyst regeneration in transition-metal-mediated atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions. Eur. J. Inorg. Chem., 2010, 2449–2460, 10.1002/ejic.201000234.
Muñoz-Molina, J.M., Belderrain, T.R., Pérez, P.J., Atom transfer radical reactions as a tool for olefin functionalization – on the way to practical applications. Eur. J. Inorg. Chem., 2011, 3155–3164, 10.1002/ejic.201100379.
Severin, K., Ruthenium-catalyzed atom transfer radical addition reactions. Chimia 66 (2012), 386–388, 10.2533/chimia.2012.386.
Richel, A., Delfosse, S., Cremasco, C., Delaude, L., Demonceau, A., Noels, A.F., Ruthenium catalysts bearing N-heterocyclic carbene ligands in atom transfer radical reactions. Tetrahedron Lett. 44 (2003), 6011–6015, 10.1016/S0040-4039(03)01477-1.
Delaude, L., Demonceau, A., Noels, A.F., Ruthenium-promoted radical processes toward fine chemistry. Bruneau, C., Dixneuf, P.H., (eds.) Ruthenium Catalysts and Fine Chemistry, 2004, Springer, Berlin, Heidelberg, 155–171, 10.1007/b94645.
Severin, K., Ruthenium catalysts for the Kharasch reaction. Curr. Org. Chem. 10 (2006), 217–224, 10.2174/138527206775192915.
Borguet, Y., Richel, A., Delfosse, S., Leclerc, A., Delaude, L., Demonceau, A., Microwave-enhanced ruthenium-catalysed atom transfer radical additions. Tetrahedron Lett. 48 (2007), 6334–6338, 10.1016/j.tetlet.2007.07.029.
