In this work, the use of computational methods was essential to distinguish the three possible isomeric structures of the [RuCl3(H2O)2(Gly)] molecule. The characterization of these molecules was performed using IR, NMR and UV-VIS simulations. Some calculations related to the optimization of structures and properties such as chemical hardness and dipole moment were also conducted. The fac-cis isomer presented promising data when compared to the experimental data, indicating that this is the likely experimentally synthesized isomer. This study demonstrates the technical utility of the computational calculations by virtue of situations that prevent the realization of X-ray diffraction.
References
[1]
Chong, E., Xue, W., Storr, T., Kennepohl, P. and Schafer, L.L. (2015) Pyridonate-Supported Titanium(III). Benzylamine as an Easy-To-Use Reductant. Organometallics, 34, 4941-4945. https://doi.org/10.1021/acs.organomet.5b00469
[2]
El-Sonbati, A.Z., Diab, M.A., Shoair, A.F., El-Bindary, A.A. and Barakat, A.M. (2016) Potentiometric, Thermodynamics and Theoretical Calculations of Some Rhodanine Derivatives. Journal of Molecular Liquids, 216, 821-829.
https://doi.org/10.1016/j.molliq.2016.01.084
[3]
Sheng, H.W., Luo, W.K., Alamgir, F.M., Bai, J.M. and Ma, E. (2006) Atomic Packing and Short-To-Medium-Range Order in Metallic Glasses. Nature, 439, 419-425.
[4]
Bertoli, A.C., Garcia, J.S., Trevisan, M.G., Ramalho, T.C. and Freitas, M.P. (2016) Interactions Fulvate-Metal (Zn2+, Cu2+ and Fe2+): Theoretical Investigation of Thermodynamic, Structural and Spectroscopic Properties. BioMetals, 29, 275-285.
https://doi.org/10.1007/s10534-016-9914-8
[5]
Das, P., Sarmah, P.P., Borah, M. and Phukan, A.K. (2009) Low-Spin, Mononuclear, Fe(III) Complexes With P,N Donor Hemilabile Ligands: A Combined Experimental and Theoretical Study. Inorganica Chimica Acta, 362, 5001-5011.
https://doi.org/10.1016/j.ica.2009.08.006
[6]
de Oliveira, R.S., Boffo, E.F., Reis, F.C.C., Nikolaou, S., Andriani, K.F., Caramori, G.F. and Doro, F.G. (2016) A Ruthenium Polypyridyl Complex with the Antihypertensive Drug Valsartan: Synthesis, Theoretical Calculations and Interaction Studies with Human Serum Albumin. Polyhedron, 114, 232-241.
https://doi.org/10.1016/j.poly.2015.12.029
[7]
Bhattacharjee, J., Das, S., Reddy, T.D.N., Nayek, H.P., Mallik, B.S. and Panda, T.K. (2016) Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane-diphenylphosphanyl)amido Ligand—Synthesis, Structures, and Catalysis for Ring-Opening Polymerization of ε-Caprolactone. Zeitschrift für anorganische und allgemeine Chemie, 642, 118-127.
https://doi.org/10.1002/zaac.201500593
[8]
Chagas, M.A.S., Galvão, A.D., de Moraes, F.T., Ribeiro, A.T.B.N., de Siqueira, A.B., de Assis Salama, I.C.C., Arrais-Silva, W.W., de Sousa, K.M.D., de Sousa Pereira, C.C. and dos Santos, W.B. (2017) Synthesis, Characterization and Analysis of Leishmanicide Ability of the Compound [Ru(Cl)3(H2O)2(gly)]. Open Journal of Inorganic Chemistry, 7, 89-101. https://doi.org/10.4236/ojic.2017.74006
[9]
Salama, I.C.C.D.A. (2013) Análise Biológica Dos Compostos Rutênio, Lupeol E Boldina No Modelo Experimental Das Leishmanioses. Dissertação de Mestrado, Universidade Federal do Mato Grosso-Campus Universitário do Araguaia.
[10]
Martínez, A., Carreon, T., Iniguez, E., Anzellotti, A., Sánchez, A., Tyan, M., Sattler, A., Herrera, L., Maldonado, R.A. and Sánchez-Delgado, R.A. (2012) Searching for New Chemotherapies for Tropical Diseases: Ruthenium-Clotrimazole Complexes Display High in Vitro Activity against Leishmania Major and Trypanosoma Cruzi and Low Toxicity toward Normal Mammalian Cells. Journal of Medicinal Chemistry, 55, 3867-3877. https://doi.org/10.1021/jm300070h
[11]
Iniguez, E., Sánchez, A., Vasquez, M.A., Martínez, A., Olivas, J., Sattler, A., Sánchez-Delgado, R.A. and Maldonado, R.A. (2013) Metal-Drug Synergy: New Ruthenium(II) Complexes of Ketoconazole Are Highly Active against Leishmania Major and Trypanosoma Cruzi and Nontoxic to Human or Murine Normal Cells. Journal of Biological Inorganic Chemistry, 18, 779-790.
https://doi.org/10.1007/s00775-013-1024-2
[12]
Barbosa, M.I.F., Corrêa, R.S., de Oliveira, K.M., Rodrigues, C., Ellena, J., Nascimento, O.R., Rocha, V.P.C., Nonato, F.R., Macedo, T.S., Barbosa-Filho, J.M., Soares, M.B.P. and Batista, A.A. (2014) Antiparasitic Activities of Novel Ruthenium/Lapachol Complexes. Journal of Inorganic Biochemistry, 136, 33-39.
https://doi.org/10.1016/j.jinorgbio.2014.03.009
[13]
Koenig, P.M., Roth, R. and Dietrich, S. (2008) Lock and Key Model System. EPL, 84, 68006/68001-68006/68005. https://doi.org/10.1209/0295-5075/84/68006
[14]
Adhireksan, Z., Davey, G.E., Campomanes, P., Groessl, M., Clavel, C.M., Yu, H., Nazarov, A.A., Yeo, C.H.F., Ang, W.H., Dröge, P., Rothlisberger, U., Dyson, P.J. and Davey, C.A. (2014) Ligand Substitutions between Ruthenium-Cymene Compounds Can Control Protein versus DNA Targeting and Anticancer Activity. Nature Communications, 5, Article No. 3462. https://doi.org/10.1038/ncomms4462
[15]
Credendino, R., Poater, A., Ragone, F. and Cavallo, L. (2011) A Computational Perspective of Olefins Metathesis Catalyzed by N-Heterocyclic Carbene Ruthenium (Pre)Catalysts. Catalysis Science & Technology, 1, 1287-1297.
https://doi.org/10.1039/c1cy00052g
[16]
Wu, M., Gill, A.M., Yunpeng, L., Falivene, L., Yongxin, L., Ganguly, R., Cavallo, L. and Garcia, F. (2015) Synthesis, Structural Studies and Ligand Influence on the Stability of Aryl-NHC Stabilised Trimethylaluminium Complexes. Dalton Transactions, 44, 15166-15174. https://doi.org/10.1039/C5DT00079C
[17]
Gianferrara, T., Bratsos, I. and Alessio, E. (2009) A Categorization of Metal Anticancer Compounds Based on Their Mode of Action. Dalton Transactions, No. 37, 7588-7598. https://doi.org/10.1039/b905798f
[18]
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 Jr., J.A., Peralta, J.E., Ogliaro, F., Bearpark, M.J., Heyd, J., Brothers, E.N., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A.P., 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. and Fox, D.J. (2009) Gaussian 09. Gaussian, Inc. Print., Wallingford.
[19]
Zhao, Y. and Truhlar, D.G. (2008) The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Functionals. Theoretical Chemistry Accounts, 120, 215-241. https://doi.org/10.1007/s00214-007-0310-x
[20]
Frisch, M.J., Pople, J.A. and Binkley, J.S. (1984) Self-Consistent Molecular Orbital Methods 25. Supplementary Functions for Gaussian Basis Sets. The Journal of Chemical Physics, 80, 3265-3269. https://doi.org/10.1063/1.447079
[21]
Andrae, D., Häuβermann, U., Dolg, M., Stoll, H. and Preuβ, H. (1990) Energy-Adjustedab Initio Pseudopotentials for the Second and Third Row Transition Elements. Theoretica Chimica Acta, 77, 123-141.
https://doi.org/10.1007/BF01114537
[22]
Wolinski, K., Hinton, J.F. and Pulay, P. (1990) Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations. Journal of the American Chemical Society, 112, 8251-8260.
https://doi.org/10.1021/ja00179a005
[23]
Hashem, E., Platts, J.A., Hartl, F., Lorusso, G., Evangelisti, M., Schulzke, C. and Baker, R.J. (2014) Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study. Inorganic Chemistry, 53, 8624-8637.
[24]
Prabavathi, N., Nilufer, A., Krishnakumar, V. and Akilandeswari, L. (2012) Spectroscopic, Electronic Structure and Natural Bond Analysis of 2-aminopyrimidine and 4-aminopyrazolo[3,4-d]pyrimidine: A Comparative Study. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 96, 226-241.
https://doi.org/10.1016/j.saa.2012.05.015
[25]
Kowalczyk, I. (2014) Synthesis and Characterization of Alkylammonium Zwitterionic Amino Acids Derivatives by FTIR, NMR Spectroscopy and DFT Calculations. Acta Chimica Slovenica, 61, 39-50.
[26]
Alam, M.M., Islam, S.M.S., Rahman, S.M.M. and Rahman, M.M. (2010) Simultaneous Preparation of Facial and Meridional Isomer of Cobalt-Amino Acid Complexes and Their Characterization. Journal of Scientific Research, 2, 91-98.
[27]
Sert, Y., Ucun, F., El-Hiti, G.A., Smith, K. and Hegazy, A.S. (2016) Spectroscopic Investigations and DFT Calculations on 3-(Diacetylamino)-2-ethyl-3H quinazolin-4-one. Journal of Spectroscopy, 2016, Article ID: 5396439.
https://doi.org/10.1155/2016/5396439
[28]
Chaitanya, K. (2012) Molecular Structure, Vibrational Spectroscopic (FT-IR, FT-Raman), UV-Vis Spectra, First Order Hyperpolarizability, NBO Analysis, HOMO and LUMO Analysis, Thermodynamic Properties of Benzophenone 2,4-Dicarboxylic Acid by Ab Initio HF and Density Functional Method. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 86, 159-173.
https://doi.org/10.1016/j.saa.2011.09.069
[29]
Pearson, R.G. (2005) Chemical Hardness and Density Functional Theory. Journal of Chemical Sciences, 117, 369-377. https://doi.org/10.1007/BF02708340
[30]
Pramanik, H.A.R., Das, D., Paul, P.C., Mondal, P. and Bhattacharjee, C.R. (2014) Newer Mixed Ligand Schiff Base Complexes from Aquo-N-(2’-Hydroxy Acetophenone) Glycinatocopper(II) as Synthon: DFT, Antimicrobial Activity and Molecular Docking Study. Journal of Molecular Structure, 1059, 309-319.
https://doi.org/10.1016/j.molstruc.2013.12.009
[31]
Das, D., Dutta, A. and Mondal, P. (2015) Interaction of Aquated form of Ruthenium(III) Anticancer Complexes with Normal and Mismatch Base Pairs: A Density Functional Theoretical Study. Computational and Theoretical Chemistry, 1072, 28-36. https://doi.org/10.1016/j.comptc.2015.08.020
[32]
Shankar, R., Senthilkumar, K. and Kolandaivel, P. (2009) Calculation of Ionization Potential and Chemical Hardness: A Comparative Study of Different Methods. International Journal of Quantum Chemistry, 109, 764-771.
https://doi.org/10.1002/qua.21883
[33]
Gontrani, L., Mennucci, B. and Tomasi, J. (2000) Glycine and Alanine: A Theoretical Study of Solvent Effects upon Energetics and Molecular Response Properties. Journal of Molecular Structure: Theochem, 500, 113-127.
https://doi.org/10.1016/S0166-1280(00)00390-0
