Synthesis and Structural Characterization of Furan-2,5-dicarbonylbis(N,N-diethylthiourea) and its Dinuclear Cu(II) and Zn(II) Complexes
Main Article Content
Abstract
The condensation reaction of furan-2,5-dicarbonyl dichloride and N,N-diethylthiourea gave rise to furan-2,5-dicarbonylbis(N,N-diethylthiourea), H2L. Chemical composition and structural features of H2L were studied by spectroscopic methods as well as single crystal X-ray diffraction. H2L readily reacted with equimolar amount of CuCl2∙2H2O or ZnCl2 in MeOH with the presence of the supporting base Et3N. Such reactions resulted in metal complexes, which were characterized by spectroscopic studies. The results indicated dinuclear neutral compounds [M2(L)2] (M = Cu(II) or Zn(II)), in which H2L was doubly deprotonated and the resulting {L2–} anion bonded to metal ions through (S,O)-donor sets of the aroylthiourea moieties.
Keywords:
Aroylbis(thioureas), Cu(II) complexes, Zn(II) complexes
References
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[5] N. Selvakumaran, L. Sandhiya, N.S.P. Bhuvanesh, K. Senthilkumar, R. Karvembu, Structural diversity in aroylthiourea copper complexes - formation and biological evaluation of [Cu(I)(µ-S)SCl]2, cis-Cu(II)S2O2, trans-Cu(II)S2O2 and Cu(I)S3 cores, New J. Chem. 40 (2016) 5401-5413. https://10.1039/C5NJ03536H.
[6] Z. Ali, N.E. Richey, D.C. Bock, K.A. Abboud, J. Akhtar, M. Sher, L. McElwee-White, N,N-Disubstituted-N′-acylthioureas as modular ligands for deposition of transition metal sulfides, Dalton Trans. 47 (2018) 2719-2726. https://10.1039/C7DT04860B.
[7] K.I.Y. Ketchemen, M.D. Khan, S. Mlowe, M.P. Akerman, I. Vitorica-Yrezabal, G. Whitehead, L.D. Nyamen, P.T. Ndifon, N. Revaprasadu, P. O'Brien, Crystal structures and physicochemical studies of some novel divalent and trivalent transition metal chelates of N-morpholine-N'-benzoylthiourea, J. Mol. Struct. 1229 (2021) 129791. https://https://doi.org/10.1016/j.molstruc.2020.129791.
[8] K.R. Koch, O. Hallale, S.A. Bourne, J. Miller, J. Bacsa, Self-assembly of 2:2 metallomacrocyclic complexes of NiII and PdII with 3,3,3′,3′-tetraalkyl-1,1′-isophthaloylbis(thioureas). Crystal and molecular structures of cis-[Pd(L2-S,O)]2 and the adducts of the corresponding NiII complexes: [Ni(L1-S,O)(pyridine)2]2 and [Ni(L1-S,O)(4-dimethylaminopyridine)2]2, J. Mol. Struct. 561 (2001) 185-196. https://http://dx.doi.org/10.1016/S0022-2860(00)00924-8.
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[11] V.D. Schwade, L. Kirsten, A. Hagenbach, E.S. Lang, U. Abram, Indium(III), lead(II), gold(I) and copper(II) complexes with isophthaloylbis(thiourea) ligands, Polyhedron 55 (2013) 155-161. https://10.1016/j.poly.2013.03.008.
[12] V.D. Schwade, E.I. Teixeira, F.A. dos Santos, T. Bortolotto, B. Tirloni, U. Abram, Fluorescence studies and photocatalytic application for hydrogen production of ZnII and CdII complexes with isophthaloylbis(thioureas), New J. Chem. 44 (2020) 19598-19611. https://10.1039/D0NJ03778H.
[13] E.I. Teixeira, C.S. Schwalm, G.A. Casagrande, B. Tirloni, V.D. Schwade, Binuclear isophthaloylbis(N,N-diphenylthioureate) transition metal complexes: Synthesis, spectroscopic, thermal and structural characterization, J. Mol. Struct. 1210 (2020) 127999. https://https://doi.org/10.1016/j.molstruc.2020.127999.
[14] C.T. Pham, T.H. Nguyen, K. Matsumoto, H.H. Nguyen, CuI/CuII Complexes with Dipicolinoylbis(N,N-diethylthiourea): Structures, Magnetism, and Guest Ion Exchange, Eur. J. Inorg. Chem. 2019 (2019) 4142-4146. https://10.1002/ejic.201900865.
[15] C.D. Le, C.T. Pham, H.H. Nguyen, Zinc(II) {2}-metallacoronates and {2}-metallacryptates based on dipicolinoylbis(N,N-diethylthiourea): Structures and biological activities, Polyhedron 173 (2019) 114143-114147. https://https://doi.org/10.1016/j.poly.2019.114143.
[16] J.J. Jesudas, C.T. Pham, A. Hagenbach, U. Abram, H.H. Nguyen, Trinuclear CoIILnIIICoII Complexes (Ln = La, Ce, Nd, Sm, Gd, Dy, Er, and Yb) with 2,6-Dipicolinoylbis(N,N-diethylthiourea): Synthesis, Structures, and Magnetism, Inorg. Chem. 59 (2020) 386-395. https://10.1021/acs.inorgchem.9b02648.
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[19] A.E. Dixon, J. Taylor, III.-Acylogens and thiocarbamides, J. Chem. Soc., Trans. 93 (1908) 18-30. https://10.1039/CT9089300018.
[20] K.R. Koch, New chemistry with old ligands: N-alkyl- and N,N-dialkyl-N′-acyl(aroyl)thioureas in co-ordination, analytical and process chemistry of the platinum group metals, Coord. Chem. Rev. 216–217 (2001) 473-488. https://10.1016/S0010-8545(01)00337-X.
[21] H.H. Nguyen, C.T. Pham, A. Rodenstein, R. Kirmse, U. Abram, Bipodal Acylthiourea Ligands as Building Blocks for Bi-, Tetra-, and Polynuclear Oxorhenium(V) Complexes, Inorg. Chem. 50 (2011) 590-596. https://10.1021/ic1017642.
[22] H.H. Nguyen, J.J. Jegathesh, A. Takiden, D. Hauenstein, C.T. Pham, C.D. Le, U. Abram, 2,6-Dipicolinoylbis(N,N-dialkylthioureas) as versatile building blocks for oligo- and polynuclear architectures, Dalton Trans. 45 (2016) 10771-10779. https://10.1039/C6DT01389A.
[23] A. Rodenstein, R. Richter, R. Kirmse, Synthese und Struktur von N,N,N‴,N‴-Tetraisobutyl-N′,N″-isophthaloylbis(thioharnstoff) und Dimethanol-bis(N,N,N‴,N‴-tetraisobutyl-N′,N″-isophthaloylbis(thioureato))dicobalt(II), Z. Anorg. Allg. Chem. 633 (2007) 1713-1717. https://10.1002/zaac.200700181.
[24] C.T. Pham, M. Roca Jungfer, U. Abram, Indium(III) {2}-metallacryptates assembled from 2,6-dipicolinoyl-bis(N,N-diethylthiourea), New J. Chem. 44 (2020) 3672-3680. https://10.1039/C9NJ06420F.