4411-83-0Relevant articles and documents
Structural studies of complex compounds of 6,6'-diacetyl-2,2'-bipyridine dioxime with copper(I/II), platinum(II), and palladium(II) metal ions
Sengul, Abdurrahman,Agac, Hakan,Coban, Burak,Eroglu, Erol
, p. 25 - 36 (2011)
The tetradentate ligand 6,6'-diacetyl-2,2'-bipyridine dioxime (L) was obtained in high yield by the condensation reaction of 6,6'-diacetyl-2,2'- bipyridine with hydroxyl amine in alkaline solution. Density functional calculations and 3D modeling of the structure at the B3LYP/6-31G(d) level of theory for L revealed that the energy difference between the global trans conformer (trans-L), which possesses the C2h point group, and the distorted cis conformer (cis-L) was 5.214 kcal/mol. Synthesis and characterization of the metal complexes with Cu(I), Cu(II), Pt(II), and Pd(II) metal ions were reported. L acted as a N4- donor ligand to coordinate to the metal centers via N atoms of the 2,2'-bipyridine and the imine moieties to afford tetrahedral complex [CuI L]PF6 (1), distorted octahedral complex [CuII L(OH2)2](NO 3)2 (2), and square-planar complexes [PtII L]Cl2 (3) and [PdII L]Cl (4), respectively. The CHN analysis for 1 implies that L coordinated to 2 copper(I) ions as a bridging ligand to form a dinuclear metal complex, [Cu2L2] 2+, due to the twisting of the coordinated bonds exposed by the tetrahedral geometry preference for the metal ion. The ligand formed intramolecular hydrogen bonds between the oxime groups in 4, as revealed by the spectroscopic studies. The most stable conformations of the compounds were obtained by using the molecular mechanics optimization feature in CAChe software with an augmented MM2 force field. 1.
Complexes formed between the quadridentate, heterocyclic molecules 6,6′-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and lanthanides(III): Implications for the partitioning of actinides(III) and lanthanides(III)
Foreman, Mark R. S.,Hudson, Michael J.,Drew, Michael G. B.,Hill, Clement,Madic, Charles
, p. 1645 - 1653 (2006)
New hydrophobic, tetradentate nitrogen heterocyclic reagents, 6,6′-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridines (BTBPs) have been synthesised. These reagents form complexes with lanthanides and crystal structures with 11 different lanthanides have been determined. The majority of the structures show the lanthanide to be 10-coordinate with stoichiometry [Ln(BTBP)(NO3)3] although Yb and Lu are 9-coordinate in complexes with stoichiometry [Ln(BTBP)(NO3) 2(H2O)](NO3). In these complexes the BTBP ligands are tetradentate and planar with donor nitrogens mutually cis i.e. in the cis, cis, cis conformation. Crystal structures of two free molecules, namely C2-BTBP and CyMe4-BTBP have also been determined and show different conformations described as cis, trans, cis and trans, trans, trans respectively. A NMR titration between lanthanum nitrate and C5-BTBP showed that two different complexes are to be found in solution, namely [La(C5-BTBP)2] 3+ and [La(C5-BTBP)(NO3)3]. The BTBPs dissolved in octanol were able to extract Am(iii) and Eu(iii) from 1 M nitric acid with large separation factors. The Royal Society of Chemistry 2006.
52. Influence of Chelating Groups on the Luminescence Properties of Europium(III) and Terbium(III) Chelates in the 2,2'-Bipyridine Series
Mukkala, Veli-Matti,Kwiatkowski, Marek,Kankare, Jouko,Takalo, Harri
, p. 893 - 899 (1993)
Eight different 2,2'-bipyridine derivatives, i.e. 2, 5, 8, 10, 12, 13, 15, and 19 (Schemes 1 and 2), were prepared to study the influence of the chelating groups on the luminescence properties of their EuIII and TbIII chelates.According to our luminescence results, 2,2'-(methylenenitrilo)bis(acetic acid) as well as (methylenenitrilo)bis(methylphosphonic acid) in 6- and 6'-position of 2,2'-bipyridine is a suitable group when developing luminescent markers for bioaffinity assays based on time-resolved luminescence measurement.
Design and synthesis of new Ru-complexes as potential photo-sensitizers: Experimental and TD-DFT insights
Sharmoukh,Hassan, Walid M. I.,Gros, Philippe C.,Allam, Nageh K.
, p. 69647 - 69657 (2016)
We report density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations on a novel organic ligand and a novel class of ruthenium complexes; cis-RuL2X2 with L = 2,2′-bipyridine-6,6′-bis ethyl ester phosphonate and phosphonic acid, X = Cl, CN or NCS. The calculations show that cis-configurations are more stable than the trans-counterparts. The DFT results have been used to help design such novel complexes for potential use as sensitizers. We demonstrate the opportunity to synthesize such complexes with high purity. The synthesis of these complexes relies on the preparation of the key intermediates cis-Ru(2,2′-bipyridine-6,6′-bisdiethyl ester phosphonate)Cl2. These complexes were characterized by 1H, 13C, and 31P NMR, elemental analysis and FTIR spectroscopy. The NCS complex shows the smallest optical band gap followed by the Cl and CN complexes, respectively, with the highest performance upon use as a sensitizer in dye-sensitized solar cells.
Models of molecular photocatalysts for water oxidation: Strategies for conjugating the Ru(bda) fragment (bda = 2,2′-bipyridine-6,6′-dicarboxylate) to porphyrin photosensitizers
Adamo, F.,Alessio, E.,Iengo, E.,Vidal, A.
, (2021)
Model dyads, in which the Ru(bda) water oxidation catalyst (WOC) is connected to a porphyrin, were prepared following two different modular strategies: i) the direct linkage approach, in which porphyrins bearing peripheral pyridyl rings are bound to the {
Separation and complexation of palladium(II) with a new soft N-donor ligand 6,6′-bis(5,6-dinonyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (C9-BTBP) in nitric acid medium
Zhang, Anyun,Xu, Lei,Lei, Gaoming
, p. 6374 - 6383 (2016)
Soft N-donor bis-triazine ligands developed for the separation of minor actinides (MAs) from lanthanides have been intensively studied for the past two decades. However, the investigation on the recovery and complexation of fission products Pd(ii) with these ligands has rarely been reported to date. Herein, the synthesis, and solvent extraction of Pd(ii) and some typical metals from HNO3 solutions as well as Pd(ii) complexation with a new soft N-donor ligand C9-BTBP were presented. The C9-BTBP ligand exhibited high extraction capability and high selectivity for Pd(ii) in HNO3 solution. Both 1:1 and 2:1 Pd(ii)-C9-BTBP complexes were found in solution by a combination of ESI-MS and 1H NMR titration experiments. A solid binuclear Pd(ii) complex [Pd2(NO3)4·(C9-BTBP)]·2.5H2O was synthesized and characterized by elemental analysis, DSC-TGA and 1H NMR. This is the first example that a binuclear Pd(ii) complex with any N-donor bis-triazine ligand has been confirmed both in solution and in the solid state.
Bis-(1,2,4-triazin-3-yl) ligand structure driven selectivity reversal between Am3+and Cm3+: solvent extraction and DFT studies
Ansari, S. A.,Bhattacharyya, Arunasis,Karthikeyan, N. S.,Mohapatra, P. K.,Rao, T. S.,Ravichandran, C.,Seshadri, H.,Venkatachalapathy, B.
, p. 7783 - 7790 (2021/06/16)
Selectivity between Am3+and Cm3+was investigated after their aqueous complexation with three structurally tailored hydrophilic bis-(1,2,4-triazin-3-yl) ligands followed by their extraction withN,N,N′N′-tetraoctyl diglycolamide (TODGA) dissolved in an ionic liquid (C4mim·Tf2N). The three hydrophilic ligands used were SO3PhBTP, SO3PhBTBP, and SO3PhBTPhen. It was evident from the solvent extraction studies that SO3PhBTP formed a stronger complex with Cm3+than with Am3+, but SO3PhBTPhen showed better complexation ability for Am3+than for Cm3+, and SO3PhBTBP showed no selectivity for the two actinide ions. DFT calculations indicated that the coordinating ‘N’atoms in BTP were more co-planar in the complex and this co-planarity was higher in the Cm3+complex as compared to that in Am3+. In the case of BTBP and BTPhen ligands, on the other hand, the co-planarity was more pronounced in the Am3+complexes. Mayer's bond order calculations of M-N bonds in the complexes also indicated a reversal of the complexation ability of the BTP and BTPhen ligands for Am3+and Cm3+. Calculations of the complexation energies further supported the higher selectivity of the BTP ligand for Am3+by ?52.0 kJ mol?1, and better selectivity of the BTPhen ligand for Cm3+by ?24.7 kJ mol?1
Convergent access to bis-1,2,4-triazinyl-2,2′-bipyridines (BTBPs) and 2,2′-bipyridines: Via a Pd-catalyzed Ullman-type reaction
Carrick, Jesse D.,Waters, Gabrielle D.
, p. 10807 - 10815 (2020/03/27)
Multidentate, soft-Lewis basic, complexant scaffolds have displayed significant potential in the discrete speciation of the minor actinides from the neutron-absorbing lanthanides resident in spent nuclear fuel. Efforts to devise convergent synthetic strategies to targets of interest to improve liquid-liquid separation outcomes continue, but significant challenges to improve solubility in process-relevant diluents to effectively define meaningful structure-activity relationships remain. In the current work, a synthetic method to achieve the challenging 2,2′-bipyridine bond of the bis-1,2,4-triazinyl-2,2′-bipyridine (BTBP) complexant class leveraging a Pd-catalyzed Ullman-type coupling is reported. This convergent strategy improves upon earlier work focused on linear synthetic access to the BTBP complexant moiety. Method optimization, relevant substrate scope and application, as well as a preliminary mechanistic interrogation are reported herein.
Uranyl Complexes with Aroylbis(N, N-dialkylthioureas)
Noufele, Christelle Njiki,Pham, Chien Thang,Hagenbach, Adelheid,Abram, Ulrich
, p. 12255 - 12269 (2018/09/27)
The reaction of isophthaloylbis(N,N-diethylthiourea), H2L1, with UO2(CH3COO)2·2H2O and NEt3 as a supporting base gives a tetranuclear, anionic complex of the composition [{UO2(L1)}4(OAc)2]2-, in which the uranyl ions are S,O-chelate bonded. Each two of them are additionally linked by an acetato ligand. Similar reactions of various uranyl starting materials (uranyl acetate, uranyl nitrate, (NBu4)2[UO2Cl4]) with corresponding pyridine-centered ligands (pyridine-2,6-dicarbonylbis(N,N-dialkylthioureas), H2L2) yield mononuclear, neutral compounds, in which the thiourea derivatives are coordinated as S,N,N,N,S-five-dentate chelators. The equatorial coordination spheres of the formed hexagonal bipyramidal complexes [UO2(L2)(solv)] are completed by solvent ligands (H2O, MeOH, or DMF). Attempted reactions without a supporting base result in decomposition of the organic ligands and the formation of hexanuclear uranyl complexes with pyridine-2,6-dicarboxylato ligands, while the use of an excess of base results in condensation and the formation of dinuclear [{UO2(L2)(μ-OMe)}2]2- complexes. A stable complex of the composition [UO2(L3)] results from reactions of common uranyl starting materials with 2,2′-bipyridine-6,6′-dicarbonylbis(N,N-diethylthiourea) (H2L3). The equatorial coordination sphere of the neutral, hexagonal bipyramidal complex is occupied by an SN4S donor atom set, which is provided by the hexadentate organic ligand. While the uranium complexes with {L1}2- and {L2}2- are labile and rapidly decompose in acidic solutions, [UO2(L3)] is stable over a wide pH range, and the ligand readily extracts uranyl ions from aqueous solutions into organic solvents.
Na2(smbipy) - A bipyridine-derived ligand with chelating sulfonate tags and its 3d metal complexes
Oelkers, Benjamin
, p. 5838 - 5848 (2015/02/02)
The sulfonated bipyridine derivative disodium 6,6′-bis(sulfonatomethyl)-2,2′-bipyridine [Na2(smbipy)] was synthesized, and its complexation behaviour towards divalent 3d metals in aqueous solution was explored. The complexes of late 3d metals [M(smbipy)(H2O)2]·H2O (M = Co, Ni, Zn) and [Cu(smbipy)(H2O)] are sparingly soluble in water, and their crystal structures show fourfold equatorial coordination (κ4N,N',O,O') of the smbipy ligand. Ammonia-rich solutions of the NiII and CuII aqua complexes yield the decomplexation products [Ni(NH3)6](smbipy), [Ni(NH3)5(H2O)](smbipy) and [Cu(NH3)4](smbipy)·2H2O. Buffered solutions with a reduced ammonia content lead to [Ni(smbipy)(NH3)2] and [Cu(smbipy)(NH3)3]·2H2O, and the latter shows twofold coordination of the smbipy ligand through the nitrogen atoms only (κ2N,N'). When nearly quantitative amounts of ammonia are applied, two closely related complexes with the core motif [(smbipy)Cu(μ-OH)2Cu] form. Crystal structures of all complexes were obtained, and their features are discussed.
