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Transition metal chelate complexes with tetrazole derived Mannich base: Metal dependent architecture and properties
Abstract
Complexes [Cu2L2Cl4], [NiL2Cl2], [PdLCl2], and [PtLCl2], where L is a novel ligand from the series of 2-subsituted 5-(α-aminoalkyl)tetrazoles, namely 5-(N,N-dimethylaminomethyl)-2-tert-butyltetrazole, have been synthesized and characterized by IR spectroscopy, thermal analysis and single crystal X-ray analysis. The complexes reported show different coordination geometries of the metals, viz. octahedral for Ni, square pyramidal for Cu, and square planar for Pt and Pd complexes. At the same time, the ligand L demonstrates the same coordination mode in all the complexes. It acts as a chelating ligand coordinated to the metal via two nitrogen atoms, namely the tetrazole ring N⁴ and the dimethylamino N atoms. Complex [PtLCl2] was found to have promising antiproliferative activity against human cervical carcinoma cells, with IC50 value being average between those of cisplatin and carboplatin. The temperature-dependent magnetic susceptibility measurements of complex [Cu2L2Cl4] revealed that the copper(II) ions were weakly antiferromagnetically coupled showing a coupling constant J of −2 cm⁻¹.
... Таким образом, поиск подходов к синтезу новых представителей этого класса азотистых гетероциклов является весьма актуальной задачей. Ранее проведены ряд исследований в области синтетической и координационной химии производных тетразола [16][17][18][19][20][21][22][23]. Настоящая работа посвящена разработке методов синтеза новых представителей мультитопных тетразолсодержащих лигандов с использованием преимущественно классических методов органической химии. ...
Drawing the experience of 5-phenyl- and 5-pyridyltetrazoles, it was shown that classical nitration-reduction methods in combination with typical alkylation reactions of tetrazole derivatives can be used to obtain multitopic polynuclear tetrazole-containing ligands. Methods for the preparation of a number of previously undescribed polynuclear tetrazole derivatives, including those combining both tetrazole and pyridine rings in the molecule, have been developed. The composition and structure of the obtained compounds were determined by elemental analysis, single crystal X-ray diffraction, NMR and IR spectroscopy. For (5-(pyridin-2-yl)tetrazol-2-yl)(5-(pyridin-2-yl)tetrazol-1-yl)methane the crystalline structure was determined and it was found that this compound forms a 3D polymer framework due to non-classical hydrogen bonds. In its crystal structure there is a network of π – π stacking interactions between tetrazole rings of neighbouring molecules, as well as between pyridine rings.
In this chapter, the tetrazoles investigations between 2009 and 2019 are summarized. Emphasis is made on the publications reported in 2017–18. The attention is focused on the most important events of tetrazole chemistry such as use of new catalysts, promoters and other experimental conditions favoring processes allowing the formation and functionalization of tetrazole ring. The focus is placed on the development of safe and eco-friendly methods to access tetrazoles. A special section of the review is devoted to the coordination chemistry of tetrazole, which is developing recently. The most important achievements reporting the use of tetrazoles as energetic materials and in medicinal chemistry are highlighted. Strategic directions that predict the tetrazole chemistry for the next decade have been underlined.
Research topics/studies on tetrazoles and their complexes have been significantly increasing in the current century, owing to the exceptional properties of such N-heterocyclic compounds (e.g., large number of nitrogen atoms, good stability, high formation enthalpy, high dipole moment, acidity and basicity), widespread applications in coordination chemistry, medicinal/biological and materials sciences, with prospects of playing a main role in functional compounds. This review aims at providing a detailed introduction to the design, preparation, properties and applications of platinum and palladium complexes derived from tetrazoles.
Novel nickel(II) and copper(II) coordination compounds with 1-tert-butyl-1H-tetrazole (L¹) and 1,5-diaminotetrazole (L²) having compositions of Ni(L¹)Cl2·H2O, Ni(L¹)2Br2·2H2O, Cu(L¹)Cl2, Cu(L¹)Br2, Ni(L²)2(C2N3)2, Cu(L²)2(C2N3)2 were synthesized. The compounds were studied using the methods of infrared and diffuse reflectance spectroscopy, single-crystal and powder X-ray diffraction, static magnetic susceptibility. Crystal structures have been determined for Cu(L¹)Br2 and Cu(L²)2(C2N3)2 complexes. Magnetic susceptibility measurements of Cu(II) and Ni(II) based complexes have revealed a wide spectrum of low-temperature magnetic states ranging from paramagnets composed of virtually isolated single magnetic ions or ferromagnetic chains to a weak ferromagnet with a remarkably strong magnetocrystalline anisotropy. 1-tert-butyl-1H-tetrazole 1,5-diaminotetrazole
1,3-Bis(1-methyl-1H-tetrazol-5-yl)propane (bmtp) was prepared by a procedure including regioselective tert-butylation of 1,3-bis(1H-tetrazol-5-yl)propane and exhaustive methylation of the obtained 1,3-bis(2-tert-butyl-1H-tetrazol-5-yl)propane, followed by removal of the tert-butyl group from the tetrazolium salt under acidic conditions. The ligand bmtp reacts with CuCl2·2H2O in ethanol to give the complexes [Cu3(bmtp)2Cl6(H2O)2]n and [Cu(bmtp)Cl2]n. The transformation of [Cu(bmtp)Cl2]n into [Cu3(bmtp)2Cl6(H2O)2]n is observed in ethanol. According to single crystal X-ray analysis, [Cu(bmtp)Cl2]n was obtained as a mixture of polymorphic forms. They are all 1D coordination polymers, in which polymeric chains include Cu2Cl4 units linked to each other by two bridging ligands via the tetrazole ring N⁴ atoms. [Cu3(bmtp)2Cl6(H2O)2]n presents a 2D coordination polymer, including Cu3Cl6 units bonded to four others by ligand molecules. In this complex, the tetrazole ligands show monodentate N⁴ and bridging N³,N⁴ coordination. The temperature-dependent magnetic susceptibility measurements of this complex revealed that the copper(II) ions are antiferromagnetically coupled, showing a coupling constant J of −4.0 cm⁻¹.
A novel N,N′‐alkylene‐bridged bis(5‐pyridyltetrazole) ligand, namely 2,5‐bis[5‐(2‐pyridyl)‐tetrazol‐2‐yl]‐2,5‐dimethylhexane (bpt), was prepared by regioselective N2‐alkylation of 5‐(2‐pyridyl)tetrazole with 2,5‐dimethylhexane‐2,5‐diol in perchloric acid. The ligand bpt was found to react with copper(II) chloride to give the dinuclear complex [Cu2(bpt)Cl4]. According to single‐crystal X‐ray analysis of the complex, bpt acts as a chelating ligand, coordinated by the metal through the tetrazole ring N4 and the pyridine ring nitrogen atoms. In the complex molecule, two copper atoms are linked by double chlorido bridges, and ligand bpt plays the role of the third bridge. The temperature‐dependent magnetic susceptibility measurements of the complex revealed that the copper(II) ions were weakly antiferromagnetically coupled showing a coupling constant J of –1.04 cm–1.
We have synthesised and characterised the dimeric copper(II) complexes [{CuCl(PzTz)}2(μ-Cl)2], [{CuCl(DMPzTz)}2(μ-Cl)2] and [{CuCl(DPhPzTz)}2(μ-Cl)2] and the monomeric complex [CuCl2(DMPzTz)] (PzTz = 2-(1-pyrazolyl)-1,3-thiazine, DMPzTz = 2-(3,5-dimethyl-1-pyrazolyl)-1,3-thiazine and DPhPzTz = 2-(3,5-diphenyl-1-pyrazolyl)-1,3-thiazine). Single crystal X-ray diffraction studies show that the geometry around the copper(II) center in the dimeric units is a distorted squared pyramid, while in the monomeric compound presents a distorted squared planar coordination. The electronic and magnetic properties of complexes are discussed on the basis of their X-ray structures and EPR spectroscopy studies combined with DFT calculations. Magnetostructural comparisons with structurally similar copper(II) complexes are also carried out. DFT calculations indicate that the dinuclear species are more stable than the mononuclear ones, although the inclusion of methyl or phenyl substituents provokes an important stabilization of the mononuclear forms. DFT calculations fail to predict the sign of the magnetic coupling constants of the complexes whereas multiconfigurational methods, CASSCF/NEVPT2 calculations, predict the correct sing of the exchange coupling constant.
Reactions of 5-substituted NH-tetrazoles with alcohols in the superacid CF3SO3H have been studied. Both the structure of the tetrazole and the nature of alcohol were found to dramatically influence the selectivity of the reaction and yields of products. Tetrazoles bearing phenyl, electron-donating aryl, or benzyl groups at the 5-position, have been alkylated using various alcohols (including MeOH and EtOH) in CF3SO3H upon heating at 60 °C for 0.3-12 h to afford 2-alkyl-2H-tetrazoles in 30-98% yields.
This review gives an insight into the recent applications of Mannich reaction and its variants in the construction of bioactive molecules. Emphasis is given to the Mannich reaction that provides bioactive molecules and/or modifies the property of an existing bioactive molecule. The role of Mannich reaction in the construction of antimalarial, antitumour, antimicrobial, antitubercular, antiinflammatory and anticonvulsant molecules and also the significance of aminoalkyl Mannich side chain on the biological property of molecules is discussed here.
Graphical Abstract
Mannich reaction plays a seminal role in the sysnthesis of numerous bioactive molecules. This review potrays applications of Mannich reaction and its variants in the construction of bioactive molecules and the role of aminoalkyl Mannich side chain on the property of bioactive/therapeutic molecules.
Alkylation of 1,5-bis(tetrazol-5-yl)-3-oxapentane with 2,5-dimethylhexane-2,5-diol in 65% aqueous perchloric acid was found to proceed selectively on the N2 atoms of both tetrazole rings generating a 15-membered macrocycle with tetrazol-2,5-diyl moieties incorporated (yield ca. 80%). Under analogous alkylation conditions 1,5-bis(1-methyltetrazol-5-yl)-3-oxapentane undergoes quaternization resulting in a macrocyclic tetrazolium perchlorate containing two 1-methyltetrazolium-3,5-diyl units linked by 3-oxapentane-1,5-diyl and 2,5-dimethylhexane-2,5-diyl bridges. Crystal structures of the macrocyclic compounds obtained, determined by single crystal X-ray analysis, are described.
The behavior of amino- and mercapto-1,2,4-triazoles in a t-BuOH–HClO4 system has been examined. Under the investigated conditions monoalkylation of 3-amino-1,2,4-triazole proceeds at the endocyclic N1 atoms whereas 1,2,4-triazole-3-thiol undergoes S-tert-butylation. Exhaustive alkylation of the above mentioned triazoles results in di-tert-butyl substituted derivatives, which give 1,3-disubstituted triazoles under the action of base. 4-Amino-1,2,4-triazole undergoes alkylation on the amino group as well as on the endocyclic N1 atom giving a 1,4-disubstituted triazolium salt. An X-ray diffraction investigation of 5-tert-butylsulfanyl-1,2,4-triazole, 1-tert-butyl-3-tert-butylamino-1,2,4-triazol-4-ium, 1-tert-butyl-3-tert-butylsulfanyl-1,2,4-triazol-4-ium, and 1-tert-butyl-4-tert-butylamino-1,2,4-triazolium perchlorates was carried out.
Complexes CuL3Cl2, PdL2Cl2 and PtL2Cl2, where L is a novel ligand from the series of 2-substituted 5-aminotetrazoles, namely 5-amino-2-tert-butyltetrazole (1), have been synthesized by the reaction of metal(II) chlorides with 1 and characterized by IR spectroscopy, thermal and X-ray analyses. The crystallographic structural analysis of these complexes revealed that 1 acts as a monodentate ligand coordinated to the metal via endocyclic N4 atom. Platinum complex demonstrates promising cytotoxicity against human cervical carcinoma cells with IC50 value average between those of cisplatin and carboplatin.
A systematic investigation of the CuCl 2 /Mebta (Mebta = 1-methylbenzotriazole) reaction system is described, involving the determination of the influence of the Cu II :Mebta ratio, the nature of solvent and the presence of counterions on the identity of the reaction products. As a consequence, complexes [Cu 2 Cl 4 (Mebta) 4 ] (1), [CuCl 2 (Mebta) 2 ] (2), {[Cu 2 Cl 4 (Mebta) 2 ]} n (3), [Cu 4 OCl 6 -(Mebta) 4 ] AE 0.25H 2 O (4 AE 0.25H 2 O) and [Cu 2 Cl 2 (Mebta) 6 ](ClO 4) 2 (5) have been isolated and structurally characterized by single-crys-tal X-ray studies. Mebta behaves as a monodentate ligand binding through N(3). 1 is a dinuclear complex, the structure of 2 consists of discrete monomeric units, and that of 3 is composed of linear, well-separated polymeric chains of Cu II atoms. The molecules of 4 AE 0.25H 2 O have a central l 4 -oxide ion surrounded tetrahedrally by four Cu II atoms. In the cations of 5 the two Cu II centres are asymmetrically bridged by two chloro ligands, with three Mebta molecules completing five coordination at each metal. Complexes were characterized by spectroscopic (IR, far-IR, solution UV/Vis) and thermal decomposition (TG, DTG, and DTA) techniques. Variable-temperature magnetic susceptibility data for 1, 3 and 5 showed intramolecular (1, 5) and intrachain (3) ferromagnetic exchange interactions. Estimates of the J parameters, experimentally derived, were in close agreement with a new magneto-structural criterion developed by us, holding for bis(l-chloro) copper(II) dimers. A comparison between the CuCl 2 /Mebta and CuBr 2 /Mebta systems is also presented. Ó 2004 Elsevier B.V. All rights reserved. Keywords: Bis(l-chloro) copper(II) dimers; EHMO calculations; Ferromagnetic exchange interactions; (l 4 -oxo)hexakis(l-chloro)tetracopper(II) core; 1-Methylbenzo triazole copper(II) complexes; One-dimensional copper(II) coordination polymers
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