Abstract
In this work, the effect of different solvents on the mechanism of the cis-to-trans isomerization of [Pd(C6Cl2F3)(I)(PH3)2] has been investigated theoretically in detail. Using a quantum mechanical approach, different pathways were investigated. A three-pathway mechanism has already been proposed which consists of two PH3-sensitive steps (k 3, k 4) and one PH3-insensitive (k diss) step. Since in the k 3 pathway the solvent has two types of explicit and implicit effects, this path was investigated for both the gas phase and solvent systems (using the PCM model). In this path, solvents with larger donor numbers (necessary condition) and smaller dielectric constant and dipole moment values (sufficient condition) are more appropriate. In the k 4 pathway, the solvent has an implicit effect only, and the smaller are the dielectric constant and dipole moment of a solvent, the more appropriate it is. To find the best solvent, a parameter, called the average activation energy, was defined, which considers the contribution of each path in the mechanism.
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Littke, A.F., Schwarz, L., Fu, G.C.: Pd/P(t-Bu)3: a mild and general catalyst for Stille reactions of aryl chlorides and aryl bromides. J. Am. Chem. Soc. 24, 6343–6348 (2002)
Miyaura, N.: In Metal-Catalyzed Cross-Coupling Reactions, 2nd edn., Diederich, F., Stang, P.J. (eds.) Wiley-VCH, New York (2004)
Miyaura, N., Suzuki, A.: Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 95, 2457–2483 (1995)
De Meijere, A., Meyer, F.E.: Fine feathers make fine birds: the Heck reaction in modern garb. Angew. Chem. Int. Ed. Engl. 33, 2379–2411 (1995)
Beletskaya, I.P., Cheprakov, A.V.: Heck reaction as a sharpening stone of palladium catalysis. Chem. Rev. 100, 3009–3066 (2000)
Stille, J.K.: The palladium-catalyzed cross coupling reactions of organotin reagents with organic electrophiles. Angew. Chem. Int. Ed. Engl. 25, 508–524 (1986)
Wolfe, J.P., Tomori, H., Sadighi, J.P., Yin, J., Buchwald, S.L.: A simple, efficient catalyst system for the palladium-catalyzed amination of aryl chlorides, bromides, and triflates. J. Org. Chem. 65, 1158–1174 (2000)
Ehrentraut, A., Zapf, A., Beller, M.: Palladium-catalyzed methoxycarbonylation of 1,3-butadiene. Adv. Synth. Catal. 344, 209–217 (2002)
Goossen, L.J., Koley, D., Hermann, H.L., Thiel, W.: Mechanistic pathways for oxidative addition of aryl halides to palladium(0) complexes: a DFT study. Organometallics 24, 2398–2410 (2005)
Casado, A.L., Espinet, P.: On the configuration resulting from oxidative addition of RX to Pd(PPh3)4 and the mechanism of the cis-to-trans isomerization of [PdRX(PPh3)2] complexes (R = aryl, X = halide). Organometallics 17, 954–959 (1998)
Akbari, A., Hoseinzade, F., Morsali, A., Beyramabadi, S.A.: Quantum mechanical study on the mechanism and kinetics of the cis-to-trans isomerization of [Pd(C6Cl2F3)I(PH3)2]. Inorg. Chim. Acta 394, 423–429 (2013)
Beyramabadi, S.A., Eshtiagh-Hosseini, H., Housaindokht, M.R., Morsali, A.: Mechanism and kinetics of the Wacker process: a quantum mechanical approach. Organometallics 27, 72–79 (2008)
Beyramabadi, S.A., Eshtiagh-Hosseini, H., Housaindokht, M.R., Morsali, A.: H-Transfer steps of the Wacker process: a DFT study. THEOCHEM 903, 108–114 (2009)
Eshtiagh-Hosseini, H., Beyramabadi, S.A., Morsali, A., Housaindokht, M.R.: O–H bond cleavage step of the Wacker process: a DFT study. THEOCHEM 941, 138–143 (2010)
Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993)
Becke, A.D.: Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098–3100 (1988)
Lee, C., Yang, W., Parr, R.G.: Development of the Colle–Salvetti conelation energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988)
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, N.J., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, Ö., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J.: Gaussian 09, Revision A.1. Gaussian, Inc., Wallingford CT (2009)
Hay, P.J., Wadt, W.R.: Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J. Chem. Phys. 82, 299–310 (1985)
Miertus, S., Scrocco, E., Tomasi, J.: Electrostatic interaction of a solute with a continuum. A direct utilization of ab initio molecular potentials for the prevision of solvent effects. Chem. Phys. 55, 117–129 (1981)
Tomasi, J., Persico, M.: Molecular interactions in solution: an overview of methods based on continuous distributions of the solvent. Chem. Rev. 94, 2027–2094 (1994)
Cammi, R., Tomasi, J.: Remarks on the use of the apparent surface charges (ASC) methods in solvation problems: iterative versus matrix-inversion procedures and the renormalization of the apparent charges. J. Comput. Chem. 16, 1449–1458 (1995)
Gutmann, V.: Empirical approach to molecular interactions. Coord. Chem. Rev. 15, 207–237 (1975)
Gutmann, V.: Solvent effects on reactivities of organometallic compounds. Coord. Chem. Rev. 18, 225–255 (1976)
Gutmann, V.: The Donor–Acceptor Approach to Molecular Interactions, p. 279. Plenum, New York (1978)
Gutmann, V.: The extension of the donor–acceptor concept. Pure Appl. Chem. 51, 2197–2210 (1979)
Kamlet, M.J., Abboud, J.-L.M., Abraham, M.H., Taft, R.W.: Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equation. J. Org. Chem. 48, 2877–2887 (1983)
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Morsali, A., Hoseinzade, F., Akbari, A. et al. Theoretical Study of Solvent Effects on the Cis-to-Trans Isomerization of [Pd(C6Cl2F3)I(PH3)2]. J Solution Chem 42, 1902–1911 (2013). https://doi.org/10.1007/s10953-013-0092-9
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DOI: https://doi.org/10.1007/s10953-013-0092-9