Complexes of AgI with cationic ligands: bis[(pyridylmethyl)ammonio]silver(I) salts

Bis­[(2-pyridyl­methyl)­ammonio]silver(I) trinitrate, [Ag(C₆H₉N₂)₂](NO₃)₃, (I), and bis{bis­[(4-pyridyl­methyl)­ammonio]silver(I)} hexakis­(perchlorate) dihydrate, [Ag(C₆H₉N₂)₂]₂(ClO₄)₆·2H₂O, (II), are rare examples of complexes with cationic ligands. In (I), the Ag⁺ cation has a T-shaped [2+1] coordination involving the pyridine N atoms and a nitrate O atom, while in (II) there are three independent two-coordinate Ag complex cations (two with the Ag atoms on independent inversion centres) and disordered ClO₄⁻ ions. The crystal structures reveal the role of hydrogen bonding in stabilizing these complexes.     

Crystallographic identification of a series of manganese porphyrin complexes with nitrogenous bases

Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme‐based protein systems, but also the catalytic properties of porphyrin‐based reaction sites in other biomimetic synthetic support environments. Unlike iron porphyrin complexes, little is known about the axial ligation behavior of Mn porphyrins, particularly in the solid state with Mn in the +3 oxidation state. Here, we present the syntheses and crystal and molecular structures of three new high‐spin manganese(III) porphyrin complexes with the different amine‐based axial ligands imidazole (im), piperidine (pip), and 1,4‐diazabicyclo[2.2.2]octane (DABCO), namely bis(imidazole)(5,10,15,20‐tetraphenylporphyrinato)manganese(III) chloride chloroform disolvate, [Mn(C₄₄H₂₈N₄)(C₃H₄N₂)₂]Cl·2CHCl₃ or [Mn(TPP)(im)₂]Cl·2CHCl₃ (TPP = 5,10,15,20‐tetraphenylporphyrin), (I), bis(piperidine)(5,10,15,20‐tetraphenylporphyrinato)manganese(III) chloride, [Mn(C₄₄H₂₈N₄)(C₅H₁₁N)₂]Cl or [Mn(TPP)(pip)₂]Cl, (II), and chlorido(1,4‐diazabicyclo[2.2.2]octane)(5,10,15,20‐tetraphenylporphyrin)manganese(III)–1,4‐diazabicyclo[2.2.2]octane–toluene–water (4/4/4/1), [Mn(C₄₄H₂₈N₄)Cl(C₆H₁₂N₂)]·C₆H₁₂N₂·C₇H₈·0.25H₂O or [Mn(TPP)Cl(DABCO)]·(DABCO)·(toluene)·0.25H₂O, (IV). A fourth complex, chlorido(pyridine)(5,10,15,20‐tetraphenylporphryinato)manganese(III) pyridine disolvate, [Mn(C₄₄H₂₈N₄)Cl(C₅H₅N)]·2C₅H₅N or [Mn(TPP)Cl(py)]·2(py), (III), acquired using different crystallization methods from published data, is also reported and compared to the previous structures.     

X-ray fluorescent and EXAFS studies of the electronic and spatial structure of dialkyl sulfides and their PdCl2 complexes in extraction systems

SK_α, SK_β, ClK_β, ClK_β, and PdL_β2 X-ray fluorescent and PdK EXAFS spectra were obtained for some organic solutions of dialkyl sulfide complexes with palladium chloride. Solvent effects on the electronic and spatial structure of complexes in solution are discussed. In the benzene solution of [PdCl₂2(C₆H₁₃)₂S], complex molecules interact with solvent molecules along a coordinate that is perpendicular to the plane of the complex molecule. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurmal Strukturnoi Khimii, Vol. 35, No. 4, pp. 105c111, July–August, 1994. Translated by L. Smolina     

Determination of kinetic parameters of inorganic metalporphyrins

The thermal properties of four heteropoly complexes α-K₃H₃[SiW₁₁Ni(H₂O)O₃₉]·11.5H₂O (I), α-K₃H₂[SiW₁₁Fe(H₂O)O₃₉]·9H₂O (II), α-[(C₄H₉)₄N]_3.5H_1.5[SiW₁₁Fe(H₂O)O₃₉]·4.5H₂O (III) and α-[(C₄H₉)₄N]_3.5H_2.5[SiW₁₁Cu(H₂O)O₃₉]·6H₂O (IV) were studied by means of TG, DTA and DSC. The activation energy and reaction order of the thermal decomposition reaction of these complexes have been calculated.

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Zusammenfassung Mittels TG, DTA und DSC wurden die thermischen Eigenschaften der vier heteropolaren Komplexe α-K₃H₃[SiW₁₁Ni(H₂O)O₃₉]·11.5H₂O (I), α-K₃H₂[SiW₁₁Fe(H₂O)O₃₉]·9H₂O (II), α-[(C₄H₉)₄N]_3.5H_1,5[SiW₁₁Fe(H₂O)O₃₉]·4.5H₂O (III) und α-[(C₄H₉)₄N]_3.5H_2,5 [SiW₁₁Cu(H₂O)O₃₉]·6H₂O (IV) untersucht. Die Aktivierungsenergie und Reaktionsordnung der thermischen Zersetzungsreaktion dieser Komplexe wurde berechnet.

     

On the structure of Pd,Pt and Rh complexes with 1,5-hexadiene

A number of halogen complexes of Pd, Pt and Rh with 1,5-hexadiene have been synthesized;three of them, C₆H₁₀PdBr₂, C₆H₁₀PtBr₂ and (C₆H₁₀RhCl)₂, for the first time. An intermediate while preparing C₆H₁₀PdCl₂ was the polynuclear polymeric moiety [C₆H₁₀(PdCl₂)₄]_n· IR, Raman and ESCA spectroscopy show that the diallylic ligand in all the complexes has the cis-configuration and that the strength of the metaldiallyl bond increases in the series Pd < Pt < Rh.     

Syntheses and structures of three macrocyclic supramolecular complexes and one ZnII‐containing coordination polymer generated from a semi‐rigid multidentate N‐containing ligand

Semirigid organic ligands can adopt different conformations to construct coordination polymers with more diverse structures when compared to those constructed from rigid ligands. A new asymmetric semirigid organic ligand, 4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine ( L ), has been prepared and used to synthesize three bimetallic macrocyclic complexes and one coordination polymer, namely, bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[dichloridozinc(II)] dichloromethane disolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( I ), the analogous chloroform monosolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·CHCl₃, ( II ), bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[diiodidozinc(II)] dichloromethane disolvate, [Zn₂I₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( III ), and catena‐poly[[[diiodidozinc(II)]‐μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine] chloroform monosolvate], {[ZnI₂(C₁₂H₁₀N₆)]·CHCl₃}_n, ( IV ), by solution reaction with ZnX₂ (X = Cl and I) in a CH₂Cl₂/CH₃OH or CHCl₃/CH₃OH mixed solvent system at room temperature. Complex ( I ) is isomorphic with complex ( III ) and has a bimetallic ring possessing similar coordination environments for both of the Zn^II cations. Although complex ( II ) also contains a bimetallic ring, the two Zn^II cations have different coordination environments. Under the influence of the I^? anion and guest CHCl₃ molecule, complex ( IV ) displays a significantly different structure with respect to complexes ( I )–( III ). C—H…Cl and C—H…N hydrogen bonds, and π–π stacking or C—Cl…π interactions exist in complexes ( I )–( IV ), and these weak interactions play an important role in the three‐dimensional structures of ( I )–( IV ) in the solid state. In addition, the fluorescence properties of L and complexes ( I )–( IV ) were investigated.     

Transition-metal complexes with bidentate ligands spanning trans-positions. V. Crystal and molecular structures of complexes [RhCl(CO) (1)] and [PdCl2(1)]; 1 = 2,11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene

The structures of [RhCl(CO) ( 1 )] and [PdCl₂ ( 1 )], where 1 is the bidentate ligand (C₆H₅)₂P·CH₂·C₁₈H₁₀· CH₂·P(C₆H₅)₂, have been determined from threedimensional X-ray counter data collected on single crystals of the C₆H₅·CN solvates. The two compounds are isomorphous and crystallize in the triclinic system, space group P 1 , Z = 2: a = 14.580 (8), b = 13.029 (10), c = 11.909 (6) Å, α = 106.33 (5), β = 100.47 (4), γ = 95.73 (5)° for the rhodium complex; a = 14.361 (5), b = 13.044 (7), c = 11.897 (4) Å, α = 105.97 (4), β = 100.27 (3), γ = 94.76 (4)°, for the palladium complex. In both complexes the metal atom is four-coordinate with slightly distorted square-planar configuration. In both cases the ligand 1 spans trans positions with M-P bond lengths in the ranges of the literature data. Also the other bond distances fall in regular ranges. Ligand 1 has almost the same conformation in both complexes and is characterized by a strong out-of-plane deformation of the benzophenanthrene system as a consequence of severe overcrowding.     

Cyclische Ester des dreiwertigen Arsens und Antimons

Cyclic Esters of Trivalent Arsenic and Antimony 2,2′-Dihydroxybiphenyl, 2,2′-dihydroxybinaphthyl, and o-mercapto-phenol react with AsCI₃ and SbCI₃ giving the chelate complexes (C₁₂H₈O₂)MCI, (C₂₀H₁₂O₂)MCI (M = As, Sb), and (C₆H₄OS)AsCl. By interaction of pyrocatechol, 2,2′-di- hydroxybiphenyl. and 2,2′-dihydroxybinaphthyl with AsCl, in presence of amines the complexes amin · H[As(C₅H₄O₂)₂], amin · H[As(C₁₂H₈O₂)₂], and amin · H[As(C₂₀H₁₂O₂)₂] are obtained.     

Palladium(II) halide complexes with 2,5-dimethyl-, 2-amino-, 2-amino-5-methyl-, 2-ethylamino- and 2-mercapto-5-methyl-1,3,4-thiadiazole

Some palladium(II) halide complexes with 2,5-dimethyl- (DTZ), 2-amino- (ATZ), 2-amino-5-methyl- (MATZ), 2-ethylamino- (EATZ) and 2-mercapto-5-methyl-1,3,4-thiadiazole (MTTZ) have been prepared and studied: PdX₂ · 2L (L = DTZ, ATZ, MATZ : X = Cl, Br, I; L = EATZ: X = Br, I; L = MTTZ: X = I), PdCl₂ · 2.5EATZ, PdCl₂ · 3MTTZ, PdBr₂ · 1.5MTTZ and PdX₂ · L (L = DTZ, ATZ, MATZ, EATZ: X = Cl, Br; L = MTTZ: X = Cl(H₂O), Br). In the PdX₂ · 2L, PdCl₂ · 2.5EATZ and PdCl₂ · 3MTTZ complexes the palladium ions are cis-(2X, 2L)-coordinated, the coordination sites being N_ring for DTZ, NR₂ for ATZ, MATZ, EATZ and C = S for MTTZ. PdBr₂ · 1.5MTTZ may be formulated as cis[PdBr₂-2L] · [PdBr₂ · L]. In the PdX₂ · L complexes the ligand very likely acts as bidentate by using a ring-nitrogen atom as the second coordination site.     

Beiträge zur Organolanthanidchemie. II. Cylopentadienyllanthanid-1,3-butadien-Komplexe – Darstellung,Eigenschaften und Reaktionen

Contributions to Organolanthanide Chemistry. II. Cyclopentadienyllanthanide 1,3-Butadiene Complexes – Synthesis, Properties, and Reactions From cyclopentadienyllanthanide dihalides and “magnesium butadiene” Cp*La(C₄H₆) · MgI₂ · 3 THF ( I ), Cp*Ce(C₄H₆) · MgBr₂ · 2 THF ( II ), Cp*Nd(C₄H₆) · MgCl₂ · 2 THF ( III ), (1,3-(t-C₄H₉)₂C₅H₃)Nd(C₄H₆) · MgCl₂ · 2 THF ( IV ), CpEr(C₄H₆) · MgCl₂ · 2 THF ( V ) and (1,3-(t-C₄H₉)₂C₅H₃)Lu(C₄H₆) · MgCl₂ · 2 THF ( VI ) were obtained as highly air sensitive complexes which react easily with proton active compounds and molecules with multible bonds. The reaction products with diphenylamine and carbon dioxide Cp*Nd(NPh₂)₂ · NHPh₂ ( VII ) and Cp*Ce(O₂CC₄H₆CO₂) ( VIII ) are discribed. I–VIII were characterized by elementary analysis, i.r., ¹H and ¹³C n.m.r., and EI-MS spectra.     

Innerkomplexe mit Metallamidbindungen. II. Zink- und Chrom(II)-Komplexe des 2-[β-(Phenyl-amino)-äthyl]-pyridins

The preparation of uncharged complexes with metal amide bonds of type [MeN₄]^±0 (Me = Zn²⁺, Cr²⁺ is reported. These compounds are obtained by the interaction between Zn(C₆H₅)₂ or Cr(C₆H₅)₃ · 3 THF and 2-[β-(phenyl-amino)-ethyl]-pyridine (I). The same complexes are formed by the reaction between ZnCl₂ · 2 THF, CrBr₂ · 2 THF, or CrCl₃ · 3 THF and the lithium amide (II), which is prepared from (I) and phenyl lithium. The structure of the chromium(II) complex is discussed on the basis of magnetic and visible absorption measurements.     

Synthesis and structures of 11,11,12,12‐tetracyano‐2,6‐diiodo‐9,10‐anthraquinodimethane and its 2:1 cocrystals with anthracene,pyrene and tetrathiafulvalene

Radical salts and charge‐transfer complexes (CTCs) containing tetracyanoquinodimethane (TCNQ) display electrical conductivity, which has led to the development of many TCNQ derivatives with enhanced electron‐accepting properties that are applicable toward organic electronics. To expand the family of TCNQ derivatives, we report the synthesis and structures of 11,11,12,12‐tetracyano‐2,6‐diiodo‐9,10‐anthraquinodimethane (abbreviated as DITCAQ), C₂₀H₆I₂N₄, and its charge‐transfer complexes with various electron donors, namely DITCAQ–anthracene (2/1), C₂₀H₆I₂N₄·0.5C₁₄H₁₀, (I), DITCAQ–pyrene (2/1), C₂₀H₆I₂N₄·0.5C₁₆H₁₀, (II), and DITCAQ–tetrathiafulvalene (2/1), C₂₀H₆I₂N₄·0.5C₆H₄S₄, (III). The molecular structure of DITCAQ consists of a 2,6‐diiodo‐9,10‐dihydroanthracene moiety with two malononitrile substituents. DITCAQ possesses a saddle shape, since the malononitrile groups bend significantly up out of the plane of the central ring and the two benzene rings bend down out of the same plane. π–π interactions between DITCAQ and the electron‐donor molecules control the degree of charge transfer in cocrystals (I), (II), and (III), which is reflected in both the dihedral angles between the terminal benzene ring and the central ring on the DITCAQ motifs, and their corresponding IR spectra.     

Uncommon hydrogen bonds between a non-classical ethyl cation and π hydrocarbons: a preliminary study

This study undertakes a theoretical investigation into uncommon hydrogen bonds between the ethyl cation (C₂H₅ ⁺) and π hydrocarbons. Firstly, it considers the hyperconjugation effect of the ethyl cation, in which the non-localized hydrogen (H⁺) is taken to be a pseudoatom bound to the carbons of the methyl groups. The goal of the research is to use this electronic phenomenon to gain a better understanding of the (H⁺···π) and (H⁺···p-π) hydrogen bonds, which are considered uncommon because they are formed through the interaction of the H⁺ of the ethyl cation with the π bonds of the acetylene (C₂H₂) and ethene (C₂H₄), as well as with the pseudo-π bond of the cyclopropane (C₃H₆). In view of this, B3LYP/6-311++G(d,p) calculations were used to determine the geometries of the C₂H₅ ⁺···C₂H₂, C₂H₅ ⁺···C₂H₄, and C₂H₅ ⁺···C₃H₆ hydrogen-bonded complexes. Deformations of the bond lengths and bond angles of these systems were analyzed geometrically. Examination of the stretch frequencies and absorption intensities of the (H⁺···π) and (H⁺···p-π) hydrogen bonds has revealed red-shifts in π and p-π bonds. After structural modeling and vibrational characterization, analysis of the charge transfer following the ChelpG approach and subsequently quantification of the hydrogen bond energies (basis sets superpostition error and zero point vibrational energies being considered) were used to predict the strength of the (H⁺···π) and (H⁺···p-π) hydrogen bonds. In addition, the molecular topography was estimated using the quantum theory of atoms in molecules (QTAIM). QTAIM was chosen because of a desire to understand the (H⁺···π) and (H⁺···p-π) hydrogen bonds chemically on the basis of the quantity of charge density and interpretation of Laplacian fields. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Double complex salts [Pt(NH3)5Cl][M(C2O4)3] · n H2O (M = Fe, Co, Cr): Synthesis and study

Double complexes [Pt(NH₃)₅Cl][Fe(C₂O₄)₃] · 4H₂O, [Pt(NH₃)₅Cl][Co(C₂O₄)₃] · 2H₂O, and [Pt(NH₃)₅Cl][Cr(C₂O₄)₃] · 4H₂O were synthesized and studied by single-crystal X-ray diffraction, X-ray phase analysis, differential thermal analysis, elemental analysis, and IR spectroscopy. The crystal structures of the compounds were examined from the viewpoint of the close packing of coordination polyhedra. The thermal properties of the synthesized complexes and K₃[M(C₂O₄)₃] salts (M = Fe, Co, Cr) were compared. A procedure for the synthesis of the FePt, CoPt, and CrPt intermetallic compounds through the thermolysis of the obtained complexes was developed. Original Russian Text ? K.V. Yusenko, D.B. Vasil’chenko, A.V. Zadesenets, I.A. Baidina, Yu.V. Shubin, S.V. Korenev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1589–1593.     

Über Pentafluorphenylthio-Metallkomplexe

The compounds M(CO)₅ · THF (M = Cr, Mo, W) react with sodium mercaptide, NaSR (R = C₆F₅, C₆H₅, C₂H₅), to give the mercapto-pentacarbonylmetallate anions [M(CO)₅ · · SR]^?. The preparation of some pentafluorophenylthio complexes, e. g. [(C₆H₅)₃P]₂MSC₆F₅(M = Cu, Ag, Au), [(C₆H₅)₃P]₂Hg(SC₆F₅)₂, is reported.     

Synthesen und Eigenschaften von Pentafluorethylkupfer(I)‐ und ‐(III)‐Verbindungen: Cu(C2F5) · D, [Cu(C2F5)2]– und (C2F5)2CuSC(S)N(C2H5)2

Syntheses and Properties of Pentafluoroethylcopper(I) and ‐copper(III) Compounds: CuC₂F₅ · D, [Cu(C₂F₅)₂]^–, and (C₂F₅)₂CuSC(S)N(C₂H₅)₂ The reactions of Cd(C₂F₅)₂ · D and Zn(C₂F₅)₂ · D (D = 2 CH₃CN, 2 DMF), respectively, with copper(I) halides in the presence of halides quantitatively yield the CuC₂F₅ compounds CuC₂F₅ · D and [Cu(C₂F₅)₂]^–. The CuC₂F₅ complexes are identified by NMR spectroscopy, while [Cu(C₂F₅)₂]^– is isolated as PNP salt (PNP = (C₆H₅)₃PNP(C₆H₅)₃⁺). Both compounds are excellent C₂F₅ group transfer reagents, even at low temperature. Oxidation of [Cu(C₂F₅)₂]^– with [(C₂H₅)₂NC(S)S]₂ yields the crystalline Cu(III) compound (C₂F₅)₂CuSC(S)N(C₂H₅)₂ (monoclinic, C2/c).     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 52. Darstellung,Charakterisierung und Reaktionen von (C5H5)3Ce · THF und Na[Ce(C5H5)4] · THF

Contributions to the Chemistry of Organo Transition Metal Compounds. 52. Preparation, Characterization, and Reactions of (C₅H₅)₃Ce · THF and Na[Ce(C₅H₅)₄] · THF (C₅H₅)₃ · THF ( I ) was synthesized in a simple manner by reaction of (NH₄)₂[Ce(NO₃)₆] with C₅H₅Na. With excess C₅H₅Na the complex Na[Ce(C₅H₅)₄] · THF ( II ) could be obtained. In addition of cyclovoltammetric and polarographic measurements it was tried without success to transfer I and II into organocerium( IV ) compounds by means of different oxidizing agents. II reacts with I₂ and (C₆H₅)₃CCl forming Na[(C₅H₅)₃CeI] · THF or Na[(C₅H₅)₂CeI₂] · 4 THF and I besides of (C₆H₅)₃CCl respectively. At interaction of I with Co(acac)₃ the cobalticinium salt [(C₅H₅)₂Co][C₅H₅Ce(acac)₃] is formed. The compounds obtained were characterized by elementary analysis, hydrolysis products, magnetic moments, i.r., ¹H-n.m.r. und u.v.-vis spectra, and measurements of electric conductivity.     

New lanthanide-based complexes constructed from cucurbit[6]uril: Synthesis,structures and properties

Three lanthanide-based complexes, {Gd₂(H₂O)₁₀(CB[6])₂}·CB[6]·6Cl·12H₂O (1), {[Gd₂(H₂O)₈CB[6]₂]·(CuCl₄)·4Cl·46H₂O}_n (2), and {Dy₂(NO₃)₂(H₂O)₁₀(CB[6])}·4NO₃·14H₂O (3) (CB[6] = cucurbit[6]uril), were prepared with cucurbit[6]uril (CB[6]). These complexes were characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectroscopy, UV–Vis spectroscopy, thermogravimetric analysis and magnetization measurements. Crystallographic results showed that 1 and 3 are dinuclear and crystallize in the triclinic space group Pī, whereas 2 is a 1-D zigzag supramolecular chain that crystallizes in the monoclinic system in C2/c. The results indicated that temperature has a big effect on the supramolecular assemblies and a different structure inducer also leads to the formation of different coordination polymers. Frequency dependence in the ac susceptibility signals was observed in 3.     

Mechanism of the formation of palladium complexes serving as catalysts in hydrogenation reactions : II. Reactivity of palladium phosphine halides towards molecular hydrogen

[(PPh₃)₃(PPh₂)₂Pd₃Cl] Cl, benzene and aniline hydrochloride were isolated as products of the reactions of (PPh₃)₂PdCl₂]₂ or [(PPh₃)PdCl₂]₂ with H₂ in organic amines (Am). Similar products were obtained when (Ph₃P)₂Pd(Ph)Br was treated with H2₃ Both in amines and aromatic solvents. The reaction between H₂ and [(PBu₃)PdCl₂]₂ resulted in the formation of [(PBu₃(PBu_2)PdCl2 ·. 2 Am The kinetic data for H₂ absorption by solutions of palladium(II) complexes are consistent with the heterolytic mechanism of cleavage fo hte HH bond in the coordination sphere of palladium(II); the function of the H⁺ acceptor being performed by the bases (e.g. Am or Ph). The reaction between the palladium complexes and H₂ is autocatalytic. Reduction of the initial Pd^II complexes leads to lower oxidation state palladium complexes, which catalyse the reduction of Pd^II complexes. In the coordination sphere of the lower oxidation state palladium complexes, the oxidative addition of PR₃ to Pd takes place with formation of compounds containing a Pd-R bond. It is the reaction between these complexes and H₂ that yields palladium compounds with PR₂ ligands.     

Oxidation of a dinuclear manganese(II) complex to an oxide‐bridged dimanganese(IV) complex

Bis{μ‐2‐[bis(pyridin‐2‐ylmethyl)amino]acetato}bis[diaquamanganese(II)] bis(trifluoromethanesulfonate) monohydrate, [Mn₂(C₁₄H₁₄N₃O₂)₂(H₂O)₄](CF₃O₃S)₂·H₂O, (I), and bis{μ‐3‐[bis(pyridin‐2‐ylmethyl)amino]propionato}bis[aquamanganese(II)] bis(trifluoromethanesulfonate) dihydrate, [Mn₂(C₁₅H₁₆N₃O₂)₂(H₂O)₂](CF₃O₃S)₂·2H₂O, (II), form binuclear seven‐coordinate complexes. Oxidation of (II) with ammonium hexanitratocerate(IV), (NH₄)₂[Ce(NO₃)₆], gave the oxide‐bridged dimanganese(IV) complex di‐μ‐oxido‐bis(bis{3‐[bis(pyridin‐2‐ylmethyl)amino]propionato}manganese(IV)) bis[triaquatetranitratocerate(IV)], [Mn₂O₂(C₁₅H₁₆N₃O₂)₂][Ce(NO₃)₄(H₂O)₃]₂, (III). The manganese complexes in (II) and (III) sit on a site of symmetry.