Abstract
New mixed valence gold(III/I) salt containing two complexes [Au(Me2phen)Br2][AuBr2] (1) was prepared from the reaction of AuBr3 and 5,6-dimethyl-1,10-phenanthroline (Me2phen) in a mixture of methanol and acetonitrile. Suitable crystals of 1 for X-ray diffraction measurement were obtained by slow evaporation of the resulted red solution at room temperature. This complex was characterized by spectral methods (IR, UV–Vis and 1H NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structural analysis indicated that the asymmetric unit of 1 contains one [Au(Me2phen)Br2]+ cation and two half anions of [AuBr2]ˉ. Furthermore, the packing diagram of this complex, 3-D structure stabilized by intermolecular Au…Br and Au…π interactions and intermolecular C–H···Br hydrogen bonds. The experimental investigations on complex have been accompanied computationally by the density functional theory (DFT) and time-dependent DFT calculations. The nature of the Au–N bonds was investigated using quantum theory of atoms in molecules. Moreover, natural bond orbital analysis carried out to obtain hyper-conjugative interactions and electron delocalization on the complex.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abedi A, Amani V, Safari N (2012) Indium(III) hetero-ligand complexes containing 1,10-phenanthroline, chloride, acetonitrile and dimethyl sulfoxide: crystal structure determination, and luminescent properties. Main Group Chem 11:223–233. https://doi.org/10.3233/MGC-2012-0075
Ahmadian I, Abedi A, Amani V, Safari N (2015) Structure and luminescence properties of trichloridothallium(III) complexes with phenanthroline derivatives. Res Chem Intermed 41:2971–2983. https://doi.org/10.1007/s11164-013-1405-8
Alizadeh R, Hafezeffati S, Amani V, Khavasi HR, Harms K (2015) Synthesis, characterization, crystal structure determination, and luminescence properties of two new gold(III) complexes with phenanthridine ligand. Monatshefte für Chemie Chem Mon 146:581–589. https://doi.org/10.1007/s00706-014-1348-9
Amani V (2018) Synthesis, characterization and crystal structure determination of dibromido(5,5′-dimethyl-2,2′-bipyridine)gold(III)tetrabromidoaurate(III) complex. J Appl Chem (Accepted for publication)
Amani V, Abedi A, Ghabeshi S, Khavasi HR, Hosseini SM, Safari N (2014) Synthesis and characterization of a series of gold(III) complexes with the 4,4′-dimethyl-2,2′-bipyridine ligand: counterion influence on the cytotoxicity of gold(III) complexes. Polyhedron 79:104–115. https://doi.org/10.1016/j.poly.2014.04.064
Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91:893–928. https://doi.org/10.1021/cr00005a013
Biegler-Konig F, Schonbohm J, Bayles D (2001) AIM2000-a program to analyze and visualize atoms in molecules. J Comput Chem 22:545–559. https://doi.org/10.1002/1096-987X(20010415)22:5<545::AIDJCC1027>3.0.CO;2-Y
Bostancioglu RB, Kaya M, Koparal AT, Benkli K (2016) Gold(III) compounds-mediated inhibition of lung cancer cell proliferation. Anticancer Drugs 27:225–234. https://doi.org/10.1097/cad.0000000000000327
Braunstein P, Clark RJH (1973) The preparation, properties, and vibrational spectra of complexes containing the AuCl2 −, AuBr −2 , and AuI2 − ions. J Chem Soc Dalton Trans 1845–1848. https://doi.org/10.1039/dt9730001845
Bruker (1998) SMART and SAINT. Bruker AXS Inc., Madison, WI, USA
Delbari AS, Shahvelayati AS, Jodaian V, Amani V (2015) Mononuclear and dinuclear indium(III) complexes containing methoxy and hydroxy-bridge groups, nitrate anion and 4,4′-dimethyl-2,2′-bipyridine ligand: synthesis, characterization, crystal structure determination, luminescent properties, and thermal analyses. J Iran Chem Soc 12:223–232. https://doi.org/10.1007/s13738-014-0477-8
Döring C, Jones PG (2013) Bis(4-picoline-kN)gold(I) dibromidoaurate(I) and bis(4-picoline-kN)gold(I) dichloridoaurate(I): space-group ambiguity?. Acta Crystallogr Sect C 69:709–711. https://doi.org/10.1107/s0108270113015047
Espinosa E, Alkorta I, Elguero J, Molins E (2002) From weak to strong interactions: a comprehensive analysis of the topological and energetic properties of the electron density distribution involving X–H···F–Y systems. J Chem Phys 117:5529–5542. https://doi.org/10.1063/1.1501133
Foroutan-Nejad C, Shahbazian S, Marek R (2014) Toward a consistent interpretation of the QTAIM: tortuous link between chemical bonds, interactions, and bond/line paths. Chem Eur J 20:10140–10152. https://doi.org/10.1002/chem.201402177
Frisch MJ, Trucks GW, 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 M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery 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 O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09 (Revision A1). Gaussian Inc., Wallington
Geldmacher Y, Rubbiani R, Wefelmeier P, Prokop A, Ott I, Sheldrick WS (2011) Synthesis and DNA-binding properties of apoptosis-inducing cytotoxic half-sandwich rhodium(III) complexes with methyl-substituted polypyridyl ligands. J Organomet Chem 696:1023–1031. https://doi.org/10.1016/j.jorganchem.2010.10.034
Gholivand K, Mahzouni HR, Esrafili MD (2012) Structure, bonding, electronic and energy aspects of a new family of early lanthanide (La, Ce and Nd) complexes with phosphoric triamides: insights from experimental and DFT studies. Dalton Trans 41:1597–1608. https://doi.org/10.1039/C1DT11084E
Glisic BD et al (2016) Synthesis, structural characterization and biological evaluation of dinuclear gold(III) complexes with aromatic nitrogen-containing ligands: antimicrobial activity in relation to the complex nuclearity. MedChemComm 7:1356–1366. https://doi.org/10.1039/c6md00214e
Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J Chem Phys 82:299–310. https://doi.org/10.1063/1.448975
Jagadeesan S, Balasubramanian V, Baumann P, Neuburger M, Häussinger D, Palivan CG (2013) Water-soluble Co(III) complexes of substituted phenanthrolines with cell selective anticancer activity. Inorg Chem 52:12535–12544. https://doi.org/10.1021/ic4016228
Kepert CM, Bond AM, Deacon GB, Spiccia L, Skelton BW, White AH (2004) The synthesis and structure of heteroleptic tris(diimine)ruthenium(II) complexes. Dalton Trans 1766–1774. https://doi.org/10.1039/b401761g
Keyvani ZA, Shahbazian S, Zahedi M (2016) To what extent are “Atoms in Molecules” structures of hydrocarbons reproducible from the promolecule electron densities? Chem A Eur J 22:5003–5009. https://doi.org/10.1002/chem.201504862
Macias FJ et al (2015) Synthesis and analysis of the structure, diffusion and cytotoxicity of heterocyclic platinum(IV) complexes. Chem Eur J 21:16990–17001. https://doi.org/10.1002/chem.201502159
Martinez-Lillo J, Armentano D, De Munno G, Julve M, Lloret F, Faus J (2013) Ferromagnetic coupling and spin canting behaviour in heterobimetallic ReIVMII/III (M=CoII/III, NiII) species. Dalton Trans 42:1687–1695. https://doi.org/10.1039/C2DT31546G
McGee KA, Marquardt BJ, Mann KR (2008) Concurrent sensing of benzene and oxygen by a crystalline salt of tris(5,6-dimethyl-1,10-phenanthroline)ruthenium(II). Inorg Chem 47:9143–9145. https://doi.org/10.1021/ic801287p
Mercury 141 (2001–2005) Copyright Cambridge Crystallographic Data Center, Cambridge, UK
Momeni BZ, Haghshenas F, Hadi S (2017) Synthesis, structural characterization and crystal structure of some dimethyltin complexes containing substituted 1,10-phenanthroline. J Mol Struct 1142:156–167. https://doi.org/10.1016/j.molstruc.2017.04.042
Olsen PM et al (2014) Synthesis, characterization, and antitumor activity of unusual pseudo five coordinate gold(III) complexes: distinct cytotoxic mechanism or expensive ligand delivery systems? J Inorg Biochem 141:121–131. https://doi.org/10.1016/j.jinorgbio.2014.08.014
O’Neill JAT, Rosair GM, Lee A-L (2012) Gold(III)-oxo complexes as catalysts in intramolecular hydroamination Catalysis. Sci Technol 2:1818–1821. https://doi.org/10.1039/C2CY20255G
Peng H, Xi Y, Ronaghi N, Dong B, Akhmedov NG, Shi X (2014) Gold-catalyzed oxidative cross-coupling of terminal alkynes: selective synthesis of unsymmetrical 1,3-diynes. J Am Chem Soc 136:13174–13177. https://doi.org/10.1021/ja5078365
Ramakrishnan S, Palaniandavar M (2008) Interaction of rac-[Cu(diimine)3]2+ and rac-[Zn(diimine)3]2+ complexes with CT DNA: effect of fluxional Cu(II) geometry on DNA binding, ligand-promoted exciton coupling and prominent DNA cleavage. Dalton Trans 3866–3878. https://doi.org/10.1039/b801497c
Ramakrishnan S, Suresh E, Riyasdeen A, Akbarsha MA, Palaniandavar M (2011) Interaction of rac-[M(diimine)3]2+ (M=Co, Ni) complexes with CT DNA: role of 5,6-dmp ligand on DNA binding and cleavage and cytotoxicity. Dalton Trans 40:3245–3256. https://doi.org/10.1039/C0DT01360A
Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor–acceptor viewpoint. Chem Rev 88:899–926. https://doi.org/10.1021/cr00088a005
Sheldrick GM (1998) SADABS. Bruker AXS, Madison, WI, USA
Sheldrick GM (2008) The SHELX programs for crystal structure determination are reviewed by their author. Acta Crystallogr Sect A 64:112–122. https://doi.org/10.1107/S0108767307043930
Tiekink ERT, Zukerman-Schpector J (2009a) Gold⋯π aryl interactions as supramolecular synthons. CrystEngComm 11:1176–1186. https://doi.org/10.1039/B901576K
Tiekink ERT, Zukerman-Schpector J (2009b) A structural survey of metal⋯π heteroaromatic supramolecular synthons for metal = tellurium, tin, and gold. CrystEngComm 11:2701–2711. https://doi.org/10.1039/B910209D
Uma Maheswari P, Rajendiran V, Stoeckli-Evans H, Palaniandavar M (2006) Interaction of rac-[Ru(5,6-dmp)3]2+ with DNA: enantiospecific DNA binding and ligand-promoted exciton coupling. Inorg Chem 45:37–50. https://doi.org/10.1021/ic050940q
Vahovska L, Potocnak I (2012) Tris(5,6-dimethyl-1,10-phenanthroline-k 2 N,N’)iron(II) bis(tricyanomethanide). Acta Crystallogr Sect E 68:m1524–m1525. https://doi.org/10.1107/s1600536812046880
Washimi M, Nishikawa M, Shimoda N, Satokawa S, Tsubomura T (2017) Blue and orange oxygen responsive emissions in the solid state based on copper(I) complexes bearing dodecafluorinated diphosphine and 1,10-phenanthroline derivative ligands. Inorg Chem Front 4:639–649. https://doi.org/10.1039/C6QI00577B
Wein AN et al (2011) Tumor cytotoxicity of 5,6-dimethyl-1,10-phenanthroline and its corresponding gold(III) complex. J Inorg Biochem 105:663–668. https://doi.org/10.1016/j.jinorgbio.2011.01.006
Acknowledgements
We would like to thank Farhangian University and Islamic Azad University, Dezful Branch for financial support.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
11696_2018_389_MOESM1_ESM.docx
Crystallographic data for the structural analyses of 1 has been deposited with the Cambridge Crystallographic Data Centre bearing the CCDC No:1570034 Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (DOCX 32 kb)
Rights and permissions
About this article
Cite this article
Sharafie, D., Amani, V. & Naseh, M. Synthesis, spectroscopic characterization, crystal structure determination and DFT calculations of [Au(Me2phen)Br2][AuBr2]. Chem. Pap. 72, 1427–1435 (2018). https://doi.org/10.1007/s11696-018-0389-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-018-0389-7