Cationic Dinuclear Complexes Research Articles

Crystal structure of cis-bis-(μ-β-alanine-κ(2) O:O')bis[tri-chlorido-rhenium(III)](Re-Re) sesquihydrate.

The structure of the title compound, [Re2Cl6(C3H7NO2)2]·1.5H2O, comprises a dinuclear complex cation [Re-Re = 2.2494 (3) Å] involving cis-oriented double carboxyl-ate bridges, four equatorial chloride ions and two weakly bonded chloride ligands in the axial positions at the two rhenium(III) atoms. In the crystal, two complex mol-ecules and two water mol-ecules constitute hydrogen-bonded dimers, while an extensive hydrogen-bonding network involving the groups of the zwitterionic ligand is important for generation of the framework. An additional partially occupied water molecule is disordered over two sets of sites about a symmetry centre with a site-occupancy ratio of 0.3:0.2.

Compound with Coexisting Mono- and Dinuclear Cu(II) Complexes Hosting a New Water Tape Cluster (H2O)22

Abstract A new compound containing mono- and dinuclear Cu(II) complexes, [Cu2(phen)2(H2O)2(OH)2] [Cu(phen)2(CO3)]2(HCO3)2 · 22H2O] (phen=1,10-phenanthroline), has been prepared and characterized by X-ray diffraction analysis, thermoanalytical techniques and temperature-dependent magnetic susceptibility measurements. The hydroxo-bridged dinuclear [Cu2(phen)2(H2O)2(OH)2]2+ complex cations and the mononuclear [Cu(phen)2(CO3)] complex molecules are assembled via π···π stacking interactions into layers. A novel water tape containing (H2O)22 cluster units has been observed in the structure of the title complex. In hydrogen bond interactions HCO3 - anions act as donor and acceptor to link the water tapes to form an infinite 2D network parallel to (010). According to the magnetic analyses, the coupling interactions in the dinuclear complex cation is ferromagnetic (J=34:5 cm-1)

Attachment of Chelating Ligand Pockets to Tinorganyl Moieties

AbstractSeveral approaches have been undertaken to realize the synthesis of a new tinorganyl compound with a 2,2′,6′,2″‐terpyridine moiety. A synthesis pathway consisting of five steps with an overall yield of 51 % was successful in producing Ph3Sn(CH2)3OPhttpy [HOttpy = 2,6‐bis(2′‐pyridyl)‐4′‐(p‐hydroxyphenyl)pyridine], and insight has been gained into (partial) halogenation reactions with this unprecedented tinorganyl compound. Halogenation with hydroiodic acid produced a new dinuclear complex cation that resulted from head‐to‐tail coordination of two monocations. Furthermore, synthesis and yields of already known intermediates have been optimized. The products were analyzed and identified by 119Sn NMR, 1H NMR, and 13C NMR spectroscopy and ESI mass spectrometry, as well as by means of single‐crystal X‐ray diffraction.

Syntheses, structures and properties of three Keggin-based metal–organic complexes derived from flexible bis-pyridyl-bis-amide and rigid phenanthroline mixed ligands

Three Keggin-type polyoxometalate (POM)-based metal–organic complexes (MOCs) constructed from mixed ligands of phenanthroline (phen) and flexible bis-pyridyl-bis-amide ligands with different spacer length: [Cu2(SiW12O40)L1(phen)2(H2O)]·3H2O (1), [Cu2(SiW12O40)L2(phen)2(H2O)4] (2) and [Cu2(SiW12O40)L3(phen)2(H2O)4]·6H2O (3) (L1=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, L2=N,N′-bis(3-pyridinecarboxamide)-1,4-butane, L3=N,N′-bis(3-pyridinecarboxamide)-1,6-hexane), have been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction analyses, elemental analyses, thermogravimetric (TG) analyses, IR spectra and powder X-ray diffraction (PXRD) analyses. Complex 1 exhibits a 2D network, in which [SiW12O40]4− (SiW12) anions act as tetradentate linkages. Complex 2 is a 0D structure containing a dinuclear complex cation [Cu2L2(phen)2(H2O)4]4+ and a discrete SiW12 anion. Complex 3 shows a 1D chain structure, in which the SiW12 anions as bidentate linkages bridge the adjacent complex cations [Cu2L3(phen)2(H2O)4]4+. The spacer lengths of the bis-pyridyl-bis-amide ligands play important roles in tuning the structures of the title complexes. In addition, the introduction of the secondary ligand phen shows significant effect on the dimensionalities of POM-based bis-pyridyl-bis-amide complexes. The electrochemical behavior and electrocatalytic properties of complex 3, as well as the photocatalytic activities of the title complexes have been studied.

Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

Abstract The reactions between elemental barium or manganese and tellurium in methylamine under solvothermal conditions at temperatures between 50 and 100 °C yield the tri‐ and ditellurides [Ba(MeNH2)3]Te3 (1) and [Mn(MeNH2)4Te2]n (2). The analogous reactions with mixtures of both metals barium and manganese lead additionally to cyanide‐containing species [Mn2(MeNH2)9(μ‐CN)(Te2)]2(Te2) (3) and [Mn2(MeNH2)10(μ‐CN)]2(Te3)3·4MeNH2 (4). Under solvothermal conditions in the presence of metallic barium and manganese methylamine partially undergoes dehydrogenation being converted to cyanide ions. In the structure of 1, Ba2+ is coordinated by three MeNH2 ligands and five tellurium atoms of surrounding Te32– anions, which are associated to infinite (Te32–)n polyanionic chains. 2 is a coordination polymer with Mn(MeNH2)4 groups connected by Te2 units to chains [Te–Te–Mn–]n. 3 and 4 are molecular compounds, consisting of cationic dinuclear complexes with almost linear Mn2+–CN–Mn2+ bridges. In the structures 2–4 manganese is in octahedral coordination.

Biological Studies of Chalcogenolato-Bridged Dinuclear Half-Sandwich Complexes

A series of cationic chalcogenolato-bridged diruthenium complexes [(η(6)-p-MeC6H4Pr(i))2Ru2(μ-EC6H5)3](+) (E = S, 1; E = Se, 2; E = Te, 3) has been obtained in ethanol from the reaction of (η(6)-p-MeC6H4Pr(i))2Ru2(μ-Cl)2Cl2 with benzenethiol, benzeneselenol, and sodium tellurophenolate, respectively. The thiolato and selenolato derivatives are isolated in good yield as the chloride salts, while the tellurolato analogue is isolated as the hexafluorophosphate salt. Similarly, the dinuclear pentamethylcyclopentadienyl (C5Me5) rhodium and iridium complexes (η(5)-C5Me5)2M2(μ-Cl)2Cl2 react with benzenethiol, benzeneselenol, and sodium tellurophenolate in ethanol to give the corresponding cationic dinuclear complexes of the general formula [(η(5)-C5Me5)2M2(μ-EC6H5)3](+) (M = Rh, E = S, 4; E = Se, 5; E = Te, 6; M = Ir, E = S, 7; E = Se, 8; E = Te, 9). In addition, cationic dinuclear complexes with mixed thiolato-selenolato and thiolato-tellurolato bridges have been prepared, [(η(6)-p-MeC6H4Pr(i))2Ru2(μ-EC6H5)(μ-SCH2C6H4-p-Bu(t))2](+) (E = Se, 10; E = Te, 11) and [(η(5)-C5Me5)2M2(μ-EC6H5)(μ-SCH2C6H5)2](+) (M = Rh, E = Se, 12; E = Te, 13; M = Ir, E = Se, 14; E = Te, 15), starting from the neutral dinuclear complexes (η(6)-p-MeC6H4Pr(i))2Ru2Cl2(μ-SCH2C6H4-p-Bu(t))2 and (η(5)-C5Me5)2M2Cl2(μ-SCH2C6H5)2. All complexes are highly cytotoxic showing activity in the submicromolar range. The nature of the chalcogenolato bridges seems to have an impact on the activity, while the nature of the metal center plays a minor role. Among the complexes tested, the dinuclear complexes 1, 4, and 7 with the thiolato bridges show the highest activity on cancer cells and the best affinity for CT-DNA as demonstrated by cell biology and biophysical experiments.

Dichlorido[6,8,22,24,34,36-hexamethyl-33,35-diaza-3,11,19,27-tetraazoniapentacyclo[27.3.1.15,9.113,17.121,25]hexatriaconta-1(33),5,7,9(34),13,15,17(35),21,23,25(36),29,31-dodecaene-κ6N3,N11,N19,N27,N33,N35]dipalladium(II) bis(perchlorate)N,N-dimethylformamide disolvate methanol disolvate

In the crystal structure of the title compound, [Pd2(C36H42N6)Cl2](ClO4)2·2C3H7NO·2CH3OH, the dinuclear PdII complex cation lies on an inversion center. Each PdII ion has a distorted square-planar coordination sphere, defined by three N atoms of the macrocyclic ligand and a chloride ion. The PdII complex cations and the methanol mol­ecules are linked through N—H⋯O and O—H⋯O hydrogen bonds, forming a zigzag chain along [101]. An intra­molecular N—H⋯Cl hydrogen bond is also observed.

Dinuclear Lanthanide(III) Complexes by Metal-Ion-Assisted Hydration of Di-2-pyridyl Ketone Azine

The initial employment of di-2-pyridyl ketone azine in 4f metal chemistry has led to a unique ligand transformation; the resulting anionic ligand is able to bridge two Ln(III) ions, affording neutral and cationic dinuclear complexes with interesting properties.

Synthesis and structural studies of mono- and dinuclear Cu(II) complexes with an ONO donor Schiff base ligand: Self-assembly and sulfato-bridged

Five Cu(II) complexes, [CuL(NO3)] (1), [CuLBr][CuLCH3OH]2Br2 (2), [CuLN3] (3), [CuL(ClO4)]2 (4) and [H2OLCu(μ-SO4)CuLH2O] (5), where L is the salicylaldehyde semicarbazone tridentate Schiff base ligand, have been synthesized and characterized by elemental analysis, FT-IR, UV–Vis and mass spectroscopy. The structures of compounds 2, 4 and 5 have been determined by single-crystal X-ray diffraction analyses. The structure of 2 contains both a mononuclear and a dinuclear species as distinct entities. The coordination geometry around the copper(II) ion in the mononuclear species is four coordinated square planar, whereas the dinuclear complex cation is five coordinated square pyramidal in which each copper(II) ion has a distorted square pyramidal geometry. In the mononuclear species, L acts as a tridentate ligand and the fourth position at the Cu ion is occupied by the Br anion, while in the dinuclear species, L acts as a bridging tridentate ligand connecting two Cu(II) ions, so there is an intramolecular copper–copper separation of 3.034Å and the apical position of each Cu ion is occupied by the oxygen of a methanol molecule. Complex 4 is a dinuclear species, in which each copper(II) ion exhibits a distorted square pyramidal geometry, which is similar to complex 2. The L ligand adopts a tridentate bridging mode with a copper–copper distance of 3.011Å. The apical position is occupied by a perchlorate anion. The molecular structure of 5 shows that it is a sulfato bridged dimeric Cu(II) complex with an intramolecular copper–copper separation of 4.733Å. The coordination geometry around each copper is five coordinated square pyramidal with two oxygen and one nitrogen atom from the tridentate ligand, L, and an oxygen from a coordinated water in equatorial positions and an oxygen from the bridging sulfato group in the axial position.

Dinuclear Cationic Zirconium Hydrides Stabilized by the N,N-Dibenzylcyclam Ancillary Ligand

The reaction of [Bn2Cyclam]ZrCl2 (Bn = benzyl) with 2 equiv of KHBEt3 generates the ionic dinuclear zirconium derivative [([Bn2Cyclam]Zr)2(μ-H)3][(Et3B)2H]. An analogous trihydride is obtained when [Bn2Cyclam]Zr(CH2Ph)2 reacts with BEt3 in the presence of dihydrogen, whereas in the absence of BEt3, the bis(ortho-metalated) derivative [(C6H4CH2)2Cyclam]Zr is obtained. DFT calculations support the stability of a cationic dinuclear trihydride complex in comparison to the neutral dinuclear tetrahydride.

Solvothermal Synthesis and Characterization of a Series of Lanthanide Thiostannates(IV): The First Examples of Inorganic–Organic Hybrid Cationic Lanthanide Thiostannates(IV)

A series of new lanthanide thiostannates(IV), [Y(2)(dien)(4)(μ-OH)(2)]Sn(2)S(6) (1, dien = diethyl-enetriamine), (tetaH)(2)[Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))]Sn(2)S(6) [Ln = Eu (2), Sm (3); teta = triethylenetetramine; tren = tris(2-aminoethyl)amine] and [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](tepa)(0.5)·H(2)O (4, tepa = tetraethylene-pentamine) were solvothermally synthesized and structurally characterized. 1 consists of a binuclear [Y(2)(dien)(4)(μ(2)-OH)(2)](4+) cation and a discrete dimeric [Sn(2)S(6)](4-) anion. Both 2 and 3 are isostructural and composed of [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+) cations, protonated triethylenetetramines (tetaH), and discrete dimeric [Sn(2)S(6)](4-) anions. A Sn(2)S(6)(4-) anion bridges two [Ln(teta)(tren)](3+) cations via the trans-S(t) (t = terminal) atoms to form the first examples of inorganic-organic hybrid thiostannate cations [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+). 4 consists of one-dimensional (1-D) neutral chains [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](n) built up from the linkage of dinuclear complex cations [Eu(2)(tepa)(2)(μ(2)-OH)(2)](4+) and bridging anions [Sn(2)S(6)](4-), free tepa molecules, and lattice water molecules. The present compounds exhibit wide-band gap semiconducting properties with absorption band edges between 2.40 and 2.91 eV.

A novel cationic dinuclear ruthenium complex: Synthesis, characterization and catalytic activity in the transfer hydrogenation of ketones

Abstract A novel cationic dinuclear ruthenium complex [RuCl(HL)(TFTPP)]2 (H2L = 2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine; TFTPP = tri(p-trifluoromethylphenyl)phosphine) has been synthesized and characterized by 31P{1H} NMR, 1H NMR, elemental analysis and X-ray crystallography. This complex is the first cationic dinuclear ruthenium complex bearing N4 ligand characterized by single crystal X-ray analysis. It exhibits good catalytic activity for the transfer hydrogenation of ketones in refluxing 2-propanol.

Syntheses and Molecular Structure of Dinuclear Transition Metal Complexes Bridged by Dipyridylamine Derivative Ligands

AbstractStable dinuclear transition metal complexes,[(η6‐C6H6)2Ru2(L1)Cl2]2+ (1), [(η6‐p‐iPrC6H4Me)2Ru2(L1)Cl2]2+ (2), [(η6‐C6Me6)2Ru2(L1)Cl2]2+ (3), [(η6‐C6H6)2Ru2(L2)Cl2]2+ (4),[(η6‐p‐iPrC6H4Me)2Ru2(L2)Cl2]2+ (5), [(η6‐C6Me6)2Ru2(L2)Cl2]2+ (6), [(η5‐C5Me5)2Rh2(L1)Cl2]2+ (7), [(η5‐C5Me5)2Ir2(L1)Cl2]2+ (8),[(η5‐C5Me5)2Rh2(L2)Cl2]2+ (9), and [(η5‐C5Me5)2Rh2(L2)Cl2]2+ (10), with the bis‐bidentate ligands 1,3‐bis(di‐2‐pyridylaminomethyl)benzene (L1) and 1,4‐bis(di‐2‐pyridylaminomethyl)benzene (L2), which contain two chelating dipyridylamine units connected by an aromatic spacer, were synthesized. The cationic dinuclear complexes were isolated as their hexafluorophosphate salts and characterized by using a combination of NMR, IR, and UV/Vis spectroscopic methods and mass spectrometry. The solid‐state structure of complex 8 as a representative was determined by X‐ray structure analysis.

The First Examples of Selenidogermanate Salts with Lanthanide Complex Counter Cations: Solvothermal Syntheses and Characterizations of [{Ln(en)3}2(μ‐OH)2]Ge2Se6 (Ln = Eu, Ho) and [{Ho(dien)2}2(μ‐OH)2]Ge2Se6

AbstractThe lanthanide selenidogermanates [{Eu(en)3}2(μ‐OH)2]Ge2Se6 (1), [{Ho(en)3}2(μ‐OH)2]Ge2Se6 (2), and [{Ho(dien)2}2(μ‐OH)2]Ge2Se6 (3) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally prepared by the reactions of Eu2O3 (or Ho2O3), germanium, and selenium in en and dien solvents respectively. Compounds 1–3 are composed of selenidogermanate [Ge2Se6]4– anion and dinuclear lanthanide complex cation [{Ln(en)3}2(μ‐OH)2]4+ (Ln = Eu, Ho) or [{Ho(dien)2}2(μ‐OH)2]4+. The [Ge2Se6]4– anion is composed of two GeSe4 tetrahedra sharing a common edge. The dinuclear lanthanide complex cations are built up from two [Ln(en)3]3+ or [Ho(dien)2]3+ ions joined by two μ‐OH bridges. All lanthanide(III) ions are in eight‐coordinate environments forming distorted bicapped trigonal prisms. In 1–3, three‐dimensional supramolecular networks of the anions and cations are formed by N–H···Se and N–H···O hydrogen bonds. To the best of our knowledge, 1–3 are the first examples of selenidogermanate salts with lanthanide complex counter cations.

Iridium(iii) soft salts from dinuclear cationic and mononuclear anionic complexes for OLED devices

Two iridium(III) soft salts based on ion-paired dinuclear cationic and mononuclear anionic complexes were designed and investigated as phosphorescent emitters for solution processed OLEDs. New dinuclear cationic complexes were prepared with two different bridging ligands, a carbazole and a phenylene spacer. Best devices were designed with the soft salt bearing a carbazole moiety.

μ-Decane-dioato-bis-[aqua-bis-(1,10-phenanthroline-κN,N')manganese(II)] dinitrate-sebacic acid-water (1/1/2).

In the title complex, [Mn2(C10H16O4)(C12H8N2)4(H2O)2](NO3)2·C10H18O4·2H2O, the asymmetric unit contains one-half of the centrosymmetric dinuclear complex cation, one uncoordinated water molecule, one-half of a free sebaic acid (decanedioic acid) molecule that is also completed by inversion symmetry, and one disordered nitrate anion [occupancy ratio 0.454 (4):0.544 (6)]. The MnII atoms are each octa­hedrally surrounded by four N atoms from two 1,10-phenanthroline (phen) ligands, one O atom from one carbonyl group of the bridging sebacate ligand and one O atom of a water mol­ecule. The crystal structure is stabilized by intermolecular O—H⋯O hydrogen bonds.

Solvothermal Syntheses, Crystal Structures, and Thermal Properties of the First Example of Selenidostannates with Mixed Ethylene Polyamine‐Coordinated Transition Metal Complexes as Counterions

AbstractThe compounds [Ni(en)3]2Sn2Se6 (1), [Ni(en)(trien)]2Sn2Se6 (2), [Co(en)(trien)]2Sn2Se6 (3), and [Ni2(trien)2(μ‐trien)]Cl4·2H2O (4) (en = ethylenediamine, trien = triethylenetetramine) were solvothermally synthesized by the reactions of NiCl2·6H2O (or CoCl2·6H2O), tin and selenium in en, mixed en/trien and trien solvents, respectively. The selenidostannates 1–3 are composed of the [Sn2Se6]4– anion and [Ni(en)3]2+ or [M(en)(trien)]2+ (M = Co, Ni) complex cations. The large dinuclear complex cation [Ni2(trien)2(μ‐trien)]4+ seems to prevent the formation of the [Sn2Se6]4– anion in the tien solvent, which indicates the different structural directing effects of the complex cations on the formation of the [Sn2Se6]4– anion. As far as we know, compounds 2 and 3 are the first examples of [Sn2Se6]4– compounds containing transition metal complexes with mixed ammine ligands. In the crystal structures of 1–4, the cations and anions are connected to three‐dimensional supramolecular networks by N–H···Se or N–H···Cl, N–H···O, and O–H···Cl hydrogen bonds.

Study of half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two di-pyridylamine units linked by an aromatic spacer

A general approach for the preparation of dinuclear η 5- and η 6-cyclic hydrocarbon platinum group metal complexes, viz. [(η 6-arene) 2Ru 2( NN∩ NN)Cl 2] 2+ (arene = C 6H 6, 1; p- iPrC 6H 4Me, 2; C 6Me 6, 3), [(η 5-C 5Me 5) 2M 2( NN∩ NN)Cl 2] 2+ (M = Rh, 4; Ir, 5), [(η 5-C 5H 5) 2M 2( NN∩ NN)(PPh 3) 2] 2+ (M = Ru, 6; Os, 7), [(η 5-C 5Me 5) 2Ru 2( NN∩ NN)(PPh 3) 2] 2+ ( 8) and [(η 5-C 9H 7) 2Ru 2( NN∩ NN)(PPh 3) 2] 2+ ( 9), bearing the bis-bidentate ligand 1,2-bis(di-2-pyridylaminomethyl)benzene ( NN∩ NN), which contains two chelating di-pyridylamine units connected by an aromatic spacer, is reported. The cationic dinuclear complexes have been isolated as their hexafluorophosphate or hexafluoroantimonate salts and characterized by use of a combination of NMR, IR and UV–vis spectroscopic methods and by mass spectrometry. The solid state structure of three derivatives, [ 2][SbF 6] 2, [ 3][PF 6] 2 and [ 4][PF 6] 2, has been determined by X-ray structure analysis.

Syntheses and crystal structures of mononuclear and dinuclear (pentamethylcyclopentadienyl)iridium(III) complexes containing 2-mercaptobenzimidazole

A reaction of [Cp*IrCl 2] 2 {Cp* = η 5-C 5(CH 3) 5} and 2-mercaptobenzimidazole (H 2bimt) in methanol in a 1:2 molar ratio gave a yellow complex of [Cp*IrCl 2(H 2bimt)]·CH 3OH ( 1). In compound 1 the H 2bimt acts as a monodentately S-donating ( κS) ligand. A similar reaction of [Cp*IrCl 2] 2 and H 2bimt in the presence of NaOCH 3 (molar ratio of 1:2:2) gave an orange product ( 2) on addition of excess amount of NH 4PF 6. Compound 2 was composed of an unsymmetrical dinuclear complex cation, [(Cp*IrCl) 2( μ-Hbimt)( μ-H 2bimt)] +, a PF 6 − anion, and water molecules of crystallization. In the complex cation, H 2bimt bridges two Ir III centers by S atom in the μ- κS: κS mode, while the monodeprotonated Hbimt − ligand bridges via S and N atoms in the μ- κS: κN 1 mode.

Bis[μ-2-(aminosulfanyl)pyridine(1−)]bis[(η5-pentamethylcyclopentadienyl)iridium(III)] diiodide

In the title dinuclear iridium(III) complex, [Ir2(C10H15)2(C5H5N2S)2]I2, the iridium(III) atoms are bridged by 2-(aminosulfanyl)pyridine(1−) [(2-py)SNH] ligands in a μ-(2-py)SNH-κ2 N(py),N(NH):κN(NH) mode. The dinuclear complex cation lies on a crystallographic inversion center, resulting in a planar Ir2N2 ring with an Ir—N(py) bond length of 2.085 (9) Å and bridging Ir—N(NH) bonds of 2.110 (9) and 2.113 (9) Å. The two (2-py)S units have mutually anti configurations with respect to the Ir2N2 ring