Facultatea de Chimie şi Tehnologie Chimică / Faculty of Chemistry and Chemical Technology
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Item Coordination compounds of copper(II) with benzoylhydrazones of substituted salicylaldehydes [Articol](2003) Samusi, Nina; Țapcov, Victor; Kerner, A.Benzoylhydrazones of 5-nitro- (H2L1), 3-nitro- (H2L2), 5-chloro- (H2L3), 5-bromo- (H2L4), and 3,5-dibromosalicylaldehydes (H 2L5) react in ethanol with copper acetate to form complexes CuL1-5. In the presence of amines (A = C5H 5N, 3-CH3C5H4N), the above reactions give complexes CuL1-5A·nH2O (n = 0, 1). When cuprous bromide or nitrate and benzoylhydrazone H2L3 were used as starting materials, complexes Cu(HL3)X (X = Br-, NO3-) were isolated. The resulting complexes all are polynuclear structures in which azomethines H2L1-5 behave as tridentate O,N,O-ligands. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (120-150°C) or deamination (150-180°C), and complete thermal decomposition (350-500°C).Item Coordination compounds of cobalt, nickel, and copper with isonitrosoacetone benzoylhydrazone [Articol](2002) Țapcov, VictorBenzoylhydrazine and isonitrosoacetone react in ethanol with cobalt, nickel, and copper halides and acetates to give the coordination compounds MX2(HL)·nH2O, MX2(HL) 2·nH2O, and ML2·nH2O [M = Co, Ni, Cu; X = Cl, Br; HL = C6H5C(O)NHNC(CH 3)CHNOH; n = 1-4]. The same reactions performed in the presence of sodium acetate and pyridine (pH 7-8) yield the complexes MLCl·nH 2O and MPy2LCl·nH2O (n = 1-4). All the complexes have a pseudooctahedral coordination geometry. The hydrazone HL behaves as a tridentate O,N,N-donor ligand. Thermolysis of the substances involves dehydration (70-90°C), deaquation (155-170°C) or deamination (175-195°C), and complete thermal decomposition (285-360°C).Item Sulfanylamide-containing coordination compounds of 3d-elements with 2,4-pentanedione bis-thiosemicarbazone and bis-4-phenylthiosemicarbazone [Articol](2008) Gulea, Aurelian; Spînu, S.; Țapcov, Victor; Poirier, DonaldThiosemicarbazide and 4-phenylthiosemicarbazide react in ethanol with 2,4-pentanedione in the presence of manganese, cobalt, nickel, copper, and zinc acetates hydrates and streptamin (Sf1), sulfaethidole (Sf 2), and sulfadimidine (Sf3) to form coordination compounds of the composition M(Sf1-3)(L1-2)·nH2O (M = Mn, Co, Ni, Cu, Zn; H2L1 is 2,4-pentanedione bis-thiosemicarbazone, H2L2 is 2,4-pentanedione bis-4-phenylthiosemicarbazone; n = 0-6). All the complexes synthesized are monomeric. Thiosemicarbazones (H2L1 and H 2L2) behave as twice deprotonated S,N,N,S-tetradentate ligands, while sulfanylamides (Sf1-3) act as monodentate ones. Thermolysis of these substances proceeds through the stages of dehydration (65-95°C) and complete thermal decomposition (430-560°C). It is found that the complex [Cu(Sf2)(L1)]·4H2O in the concentration 10-5 M inhibits the growth and fission of 100% cancer cells of the human myeloid leukemia (HL-60).Item Cobalt, nickel, and copper coordination compounds with 3-phenylpropenal benzoylhydrazone [Articol](2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX 2 • nH2O [M = Co, Ni, Cu; X = Cl, NO3, HL = C6H5CH=CHCH=NNHC(O)C6H5; n = 0, 2] and ML2 • nH2O (M = Co, Ni, Cu; n = 1-3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C5H5N, 2-CH3C5H 4N, 3-CH3C5H4N, 4-CH 3C5H4N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (145-155°C) or deamination (145-185°C), and complete thermal decomposition (330-490°C).Item Sulfanilamide-containing coordination compounds of Cu (II) with isatin and N-methylisatin thiosemicarbazones [Articol](2006) Gulea, Aurelian; Spînu, S.; Țapcov, Victor; Poirier, Donald; Roy, JennyIsatin (L1) and N-methylisatin (L2) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf1), N′- acetylsulfanilamide (Sulfacyl, Sf2), Norsulfazole (Sf3), Aethazolum (Sf4), and Sulfadimesine (Sf5) to form coordination compounds Cu(Sf1-5)L1-2X2· nH2O (X = Cl, Br; n = 2-5). All the complexes have a monomeric structure. Thiosemicarbazones L1 and L2 in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf1-5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70-95°C) and complete decomposition (410-530°C).Item Coordination compounds of cobalt, nickel, copper and zinc with thiosemicarbazone and 3-phenylpropenal semicarbazone [Articol](2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor; Ciumacov, Iurie; Roșu, TudorHydrates of 3-phenylpropenal thiosemicarbazone (HL•H2O) and semicarbazone (HL'•H2O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX2•2HL•nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO3; HL = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0-3; Solv = H2O, CH3OH], CuX2•HL• nH2O [M = Ni, Cu; n = 0, 1], ML2•nH2O and ML'•nH2O [M = Co, Ni, Zn; HL' = C6H 5CH=CH-CH=N-NHC(O)NH2; n = 0-3]. In the presence of amines (A = C5H5N, 2-CH3C5H4N, 3-CH3C5H4N, and 4-CH3C 5H4N) these reactions yield the complexes Cu(A)LCl•CH3OH and M(A)LX•nH2O [M = Cu, Ni; X = Cl, NO3; n = 0-2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL') are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70-90°C), deaquation (150-170°C), and full thermal decomposition (500-580°C).Item Coordination compounds of copper(II), nickel(II), and cobalt(II) with β-thiosemicarbazones of isatin and N-methylisatin [Articol](2004) Samusi, Nina; Țapcov, Victor; Gulea, AurelianIsatin thiosemicarbazone (HL) reacts in aquoeus-ethanolic medium with copper(II) chloride and bromide (pH 7-7.5, ethanolic KOH) to give coordination compounds CuLX·nH2O (X = Cl, Br; n = 3, 4). In the presence of amines (A = C5H5N, 3-CH3C5H 4N, and 4-CH3C5H4N), complexes CuALX·2H2O and CuA2LX·H2O (X = Cl, Br) are formed. With nickel(II) or cobalt(II) chlorides, thiosemicarbazone HL, and pyridine (1:1:3) as starting compounds, compounds MPy 2LCl·H2O (M = Ni, Co) are isolated. Under similar conditions, N-methylisatin β-thiosemicarbazone (HL') reacts with chlorides of the above-noted metals in the presence of pyridine to give complexes MPy 2L'Cl·H2O (M = Cu, Ni, Co). All the complexes are monomeric and have a pseudooctahedral structure of the coordination unit. Thiosemicarbazones HL and HL1 in these complexes behave as tridentate monodeprotonated O,N,S-ligands. Thermolysis of these substances passes through the stages of dehydration (60-90°C), deaquation (135-140°C) or deamination (160-215°C), and complete thermal decomposition (560-670°C).Item Crystal structure of copper sulfate and thiocyanate complexes with 5-bromo-and 5-nitrosalicylaldehyde thiosemicarbazones [Articol](2008) Ciumacov, Iurie; Jeanneau, Erwann; Bejenari, Natalia; Țapcov, Victor; Gulea, AurelianThe crystal structures of (5-bromosalicylidenethiosemicarbazido) aquacopper(II) sulfato(5-bromosalicylidenethiosemicarbazido)aquacuprate(II) tetrahydrate (I), (5-nitrosalicylidenethiosemicarbazido) dimethylsulfoxide(methanol)copper(II) sulfate (II), and catena(μ-thiocyanato) (5-nitrosalicylidenethiosemicarbazido)copper(II) (III) were determined. In structure I, the independent part of the unit cell contains four water molecules of crystallization and the cation-anion complex [Cu(H2O)(L)] [Cu(H2O)(L)(SO4)] containing two nonequivalent copper complexes (A and B). In these, the metal atom coordinates monodeprotonated 5-bromosalicylaldehyde thiosemicarbazone (HL) and water molecules, and in anion B also a sulfate ion. In complex ions A and B, sulfur, azomethine nitrogen, and phenolic oxygen of the salicylidene thiosemicarbazone fragment, and also water molecule form a distorted planar square around the metal atom. The axial vertex of the pyramid in anion B is occupied by the oxygen atom of the monodentate sulfate anion. In structure II, the independent part of the unit cell contains the (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) complex cation and the sulfate anion. The coordination polyhedron of the central atom is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and dimethyl sulfoxide oxygen. The axial position is occupied by the methanol oxygen atom. In structure III, the copper atom coordinates 5-nitrosalicylaldehyde thiosemicarbazone and the thiocyanate ion, which combines complexes into infinite polymer chains along the [010] direction. The copper coordination polyhedron in III is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and nitrogen of thiocyanate ion, the axial vertex is occupied by sulfur of thiocyanate ion of the neighboring complex.Item Crystal structures of nitrato-{4-bromo-2-[(2-hydroxyethylimion)methyl] phenolo}-(3,5-dibromopyridine)copper and nitrato-{2,4-dibromo-6-[(2- hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper [Articol](2006) Ciumacov, Iurie; Țapcov, Victor; Bocelli, Gabrielle; Neburger, Markus; Gulea, AurelianThe crystal structures of nitrato-{4-bromo-2-[2-hydroxyethylimino)methyl] phenolo}-(3,5-dibromopyridine)copper (I) and nitrato-{2,4-dibromo-6-[(2- hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (II) are determined. The crystals of compound I are orthorhombic: a = 14.157(3) Å, b = 15.420(3) Å, c = 17.494(4) Å, space group Pbca, Z = 8, R = 0.067. The crystals of compound II are monoclinic: a = 10.675 Å, b = 13.973 Å, c = 14.007 Å, β = 111.92°, space group P2 1/n, Z = 4, R = 0.0464. In the structures of compounds I and II, the copper atom coordinates, correspondingly, singly deprotonated 4-bromo-2-[(2-hydroxyethylimino)methyl]phenol and 2,4-dibromo-6-[(2- hydroxyethylimino)methyl]phenol molecules, and 3,5-dibromopyridine, and the nitrate ion. The coordination polyhedron of the copper ion in complexes I and II is a slightly distorted tetragonal pyramid. The bases of the pyramids are formed by the imine and pyridine nitrogen atoms and the phenolic and alcoholic oxygen atoms, and the axial vertices are occupied by the oxygen atoms of the monodentate nitrato groups. In the complexes under study, the six-membered metallocycles have asymmetric gauche conformation. In crystal, complexes I are united, due to the slip plane a, through bifurcate hydrogen bonds into infinite chains along the direction [100]. Complexes II in crystal form two-dimensional networks by means of hydrogen bonds.Item Coordination compounds of copper (II) nitrate with products of aminotris(hydroxymethyl)methane condensation with salicyl- and 5-nitrosalicylaldehydes: Synthesis and crystal structures [Articol](2005) Ciumacov, Iurie; Țapcov, Victor; Simonov, Iurie; Antoșciac, Boris; Bocelli, Gabrielle; Perrin, Monique; Starnicova, Zoia; Samusi, Nina; Gulea, AurelianThe crystal structures of copper(II) nitrate complexes with 2-(2-hydroxybenzylideneamino)-2-hydroxymethylpropane-1,3-diol (HL) and 2-hydroxymethyl-2-(2-hydroxy-5-nitrobenzylideneamino)propane-1,3-diol (HL 1) were determined. The resulting complexes were formulated as [Cu3OL3(H2O2]NO3 • 3H2O (I) and [Cu(H2O)L1]NO3 (II). The crystals of I are monoclinic, a = 17.809(4) Å, b = 30.549(6) Å, c = 18.962(4) Å, β = 115.36(3)°, space group Cc, Z = 8, R = 0.0482. Complex I is composed of two independent three-dimensional μ 3-oxo complexes; the coordination polyhedron of the copper atoms in both compounds is an elongated tetragonal bipyramid. The coordination polyhedron of the third Cu atom is a tetragonal pyramid. The bases of the pyramids are composed of the oxygen atoms of the phenol and alcohol OH groups, the imine N atom of ligand L, and μ 3-oxo atoms. The phenol and water O atoms serve as the apices in both the tetragonal bipyramids. The crystals of II are triclinic, a = 6.062(1) Å, b = 7.701(2) Å, c = 16.162(3) ̊, α = 88.15(3)°, β = 84.94(3)°, γ = 78.13(3)°, space group P1̄, Z = 2, R = 0.0272. Complex II is composed of polymer chains formed by coordination bonds between the copper atom and two O atoms of the amino alcohol in the azomethine of the neighboring complex connected to the initial one by translation along the x axis. These chains are linked through hydrogen bonds involving the oxygen atoms of the NO2 groups. The benzene rings of the azomethine ligands of the adjoining complexes from different chains are antiparallel to each other. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Its equatorial plane is formed by the phenol O atom, one of the alcohol O atoms, the N atom of ligand L1, and the O atom of the amino alcohol in the neighboring complex. The apices are the O atom of the water molecule and the O atom of the amino alcohol in the neighboring azomethine molecule. In complexes I and II, the outer-sphere nitrato group mainly serves to unite trimers and polymers in the crystal by means of hydrogen bonds.