Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas
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The structures of non-ionic [Ag(Tu)(CN)] (1) and ionic [Ag(Dmtu)2]+[Ag(CN)2]− (2) and [Ag(Imt)2]+[Ag(CN)2]− (3) silver(I) complexes, where Tu = thiourea, Dmtu = N,N′-dimethylthiourea and Imt = imidazoline-2-thione), were modeled by periodic DFT/PAW-PBE calculations; results were in good agreement with experiments. The bonding ability of the thiourea ligands (Tu, Dmtu and Imt) and the rival Ag–C, Ag–S, Ag–N and Ag–Ag bonds were estimated by natural population analysis and natural bonding orbital calculations. The metal–ligand bond strengths were found to decrease in the following order Ag-CCN > Ag-Sthiourea > Ag–NCN, and the main bonding contribution was covalent, donor–acceptor and electrostatic, respectively. The non-ionic [Ag(Tu)(CN)] complex formation [distinguished from the ionic Ag(I) complexes] was explained with the largest bonding capacity of the sulfur donor atom of Tu ligand and the strongest covalent and donor-acceptor Ag–S(Tu) interaction. The infrared (IR) spectra of the experimentally observed structures were reliably interpreted and the IR vibrations, which were sensitive to the ligand coordination to Ag(I) ion and to the weak intra- and intermolecular interactions, were selected with the help of DFT frequency calculations in the solid state.
KeywordsSilver(I) complexes Cyanide Thiourea Periodic DFT calculations
The Deanship of Scientific Research, Prince Sattam bin Abdulaziz University, Al-Kharj, Saudi Arabia is gratefully acknowledged for supporting this work through Project No. 2016/01/6822. All calculations were performed on the MADARA computer cluster of the Bulgarian Academy of Sciences.
- 10.Aslam S, Isab AA, Alotaibi MA, Saleem M, Monim-ul-Mehboob M, Ahmad S, Georgieva I, Trendafilova N (2016) Synthesis, spectroscopic characterization, DFT calculations and antimicrobial propetties of silver(I) complexes of 2,2'-bipyridine and 1,10-phenanthroline. Polyhedron 115:212–218CrossRefGoogle Scholar
- 17.Wu X, Vanderbilt D, Hamann DR (2005) Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory. Phys Rev B 72: 035105Google Scholar
- 18.Gajdos M, Hummer K, Kresse G, Furthmuller J, Bechstedt F (2006) Linear optical properties in the projector-augmented wave methodology. Phys Rev B 73: 045112Google Scholar
- 20.Frisch GWTMJ, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida TNM, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) GAUSSIA09. Gaussian Inc, Wallingford CTGoogle Scholar
- 23.Ahmad S, Saleem M, Georgieva I, Ruffer T, Schaarschmidt D, Lang H, Murtaza G, Hussain I, Habib-ur-Rehman AA, Isab MR, Malik SA (2018) Synthesis, characterization, DFT calculations and antimicrobial studies of cadmium(II) sulfate complexes of thioureas and 2-mercaptopyridine; X-ray structures of polymeric diaqua(N,N'-dimethylthiourea) sulfatocadmium(II) and bis(2-mercaptopyridine)sulfatocadmium(II). Polyhedron 149:126–133CrossRefGoogle Scholar