Synthesis and characterization of solid molybdenum(VI) complexes with glycolic,mandelic and tartaric acids. Photochemistry behaviour of the glycolate molybdenum complex

The complexes (NH₄)₂[MoO₂(C₂H₂O₃)₂]·H₂O, (NH₄)₂[MoO₂(C₈H₆O₃)₂] and (NH₄)₂[MoO₃(C₄H₄O₆)]·H₂O were prepared by reaction of MoO₃ with glycolic, mandelic and tartaric acids, respectively. The complexes were characterized by elemental and thermal analysis, IR spectroscopy and X-ray diffraction. Crystals of the glycolate and tartarate complexes are orthorhombic and the mandelate complex is monoclinic. Elemental and thermal analysis data showed that the glycolate and tartarate complexes are monohydrated. Hydration water is not present in the structure of the mandelate complex. IR spectra showed COO^? is involved in coordination as well as the oxygen atom of the deprotonated hydroxyl group of the α-carbon. The glycolate molybdenum complexes with general formula M₂[MoO₂(C₂H₂O₃)₂]·nH₂O, where M is an alkali metal and n?=?1 or ½, were also prepared and characterized. Aqueous solutions of the glycolate complex become blue and mandelate and tartarate complexes change to yellow or brown when exposed to UV-radiation.     

The novel chain‐like anion ∞1[NaMo8O26(mim)2]3− in (Hmim)3[NaMo8O26(mim)2] (mim is 1‐methylimidazole)

Tris(1‐methylimidazolium) bis(1‐methylimidazole)hexacosaoxidooctamolybdatesodium, (C₄H₇N₂)₃[NaMo₈O₂₆(C₄H₆N₂)₂], prepared from an aqueous solution containing Na₂MoO₄ and 1‐methylimidazole, contains the novel chain‐like anion _∞¹[NaMo₈O₂₆(mim)₂]^{3 −} (mim is 1‐methylimidazole). The [Mo₈O₂₆(mim)₂]⁴⁻ building unit, which lies across a center of inversion, is comprised of eight edge‐sharing MoO₆ and MoO₅(N_mim) octahedra. These molybdate units are interlinked by sodium, itself exhibiting a sixfold coordination with O atoms.     

Two new transition metal inorganic–organic hybrid borates: [tris(2‐aminoethoxy)trihydroxyhexaborato]cobalt(II) and its nickel(II) analogue

The two isomorphous title compounds, [1,5,9‐tris(2‐aminoethoxy)‐3,7,11‐trihydroxy‐3,7,11‐tribora‐1,5,9‐triborata‐2,4,6,8,10,12‐hexaoxa‐13‐oxoniatricyclo[7.3.1.0^5,13]tridecane]cobalt(II), [Co(C₆H₂₁B₆N₃O₁₃)] or Co{B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}, and the Ni^II analogue, [Ni(C₆H₂₁B₆N₃O₁₃)], each consist of an M^II cation and an inorganic–organic hybrid {B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}²⁻ anion. The M^II cation lies on a crystallographic threefold axis (as does one O atom) and is octahedrally coordinated by three N atoms from the organic component. Three O atoms covalently link the B–O cluster and the organic component. Molecules are connected to one another through N—H...O and O—H...O hydrogen bonds, forming a three‐dimensional supramolecular network.     

Experimental and theoretical study of <Superscript>13</Superscript>C shielding tensors in new-style molybdenum complex

¹³C 2D-PASS spectra of two new cis-dioxo catecholatomolybdenum complexes (NH₂CH₂NH₂CHCH₂)₂(H⁺)₃[Mo^vO ₂(C₆H₄O₂)₂] and (NH₂CH₂CH₂CH₂NH₂)₂(H⁺)₃[Mo^(v)O₂ (C₂H₂O₂)₂] have been obtained by solid-state nuclear magnetic resonance (NMR), in which the spinning sidebands were well-separated. The principal components of the ¹³C shielding tensors were extracted by theoretically fitting the intensities of ¹³C spinning sidebands. The effects of counter cations on ¹³C chemical shift isotropy and shielding tensor of cis-dioxo catecholatomolybdenum complex anion [Mo ^(v)O₂(C₆H₄O₂)₂]³⁻ were studied, comparing the ¹³C CSA of those carbon sites in complex anions with that of the counter cations. Based on the known structure of the molybdenum complex crystal, theoretical values of ¹³C shielding tensors were calculated by the ainitio GIAO method, in comparison with the experimental results.     

Synthesis and structures of cis -WO2 complexes with 2,3-dihydroxynaphthalene

{Na(OCH₃)[H₃N(CH₂)₂NH₂]₂}[WO₂(C₁₀H₆O₂)₂] (1) was obtained by the reaction of Na₂WO₄ · 2H₂O with 2,3-dihydroxynaphthalene and ethylenediamine. [H₂N(CH₂)₃NH₃]₂[WO₂(C₁₀H₆O₂)₂] (2) was synthesized by the reaction of Na₂WO₄ · 2H₂O with 2,3-dihydroxynaphthalene and 1,3-propylenediamine. Complex 1 was a one-dimensional chain-like structure and the Na atom is in the structure, while complex 2 was a discrete monomer without Na in its structure. The two complexes were synthesized in the same reaction conditions, except that protonated ethylenediamine was used in reaction 1, but 1,3-propylenediamine in reaction 2.     

Homo‐ and Heterodinuclear Ir and Rh Imine‐functionalized Protic NHC Complexes: Synthetic,Structural Studies,and Tautomerization/Metallotropism Insights

The influence of the potentially chelating imino group of imine‐functionalized Ir and Rh imidazole complexes on the formation of functionalized protic N‐heterocyclic carbene (pNHC) complexes by tautomerization/metallotropism sequences was investigated. Chloride abstraction in [Ir(cod)Cl{C₃H₃N₂(DippN=CMe)‐κN3}] ( 1 a ) (cod=1,5‐cyclooctadiene, Dipp=2,6‐diisopropylphenyl) with TlPF₆ gave [Ir(cod){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 3 a ⁺[PF₆]^?). Plausible mechanisms for the tautomerization of complex 1 a to 3 a ⁺[PF₆]^? involving C2?H bond activation either in 1 a or in [Ir(cod){C₃H₃N₂(DippN=CMe)‐κN3}₂]⁺[PF₆]^? ( 6 a ⁺[PF₆]^?) were postulated. Addition of PR₃ to complex 3 a ⁺[PF₆]^? afforded the eighteen‐valence‐electron complexes [Ir(cod)(PR₃){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 7 a ⁺[PF₆]^? (R=Ph) and 7 b ⁺[PF₆]^? (R=Me)). In contrast to Ir, chloride abstraction from [Rh(cod)Cl{C₃H₃N₂(DippN=CMe)‐κN3}] ( 1 b ) at room temperature afforded [Rh(cod){C₃H₃N₂(DippN=CMe)‐κN3}₂]⁺[PF₆]^? ( 6 b ⁺[PF₆]^?) and [Rh(cod){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 3 b ⁺[PF₆]^?) (minor); the reaction yielded exclusively the latter product in toluene at 110 °C. Double metallation of the azole ring (at both the C2 and the N3 atom) was also achieved: [Ir₂(cod)₂Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 10 ) and the heterodinuclear complex [IrRh(cod)₂Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 12 ) were fully characterized. The structures of complexes 1 b , 3 b ⁺[PF₆]^?, 6 a ⁺[PF₆]^?, 7 a ⁺[PF₆]^?, [Ir(cod){C₃HN₂(DippN=CMe)(DippN=CH)(Me)‐κ²(N3,N_imine)}]⁺[PF₆]^? ( 9 ⁺[PF₆]^?), 10? Et₂O ? toluene, [Ir₂(CO)₄Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 11 ), and 12? 2 THF were determined by X‐ray diffraction.     

Tetraalkylammonium fluorooxoperoxovanadates

Summary Compounds crystallizing from theMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄, N(C₂H₅)₄, N(C₄H₉)₄) system have been characterized by elemental analysis, vibrational spectra, and X-ray powder patterns. Besides [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) and [N(CH₃)₄]₃[V₂O₂(O₂)₄F] (2) which correspond to the known compoundsM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) and (NH₄)₃[V₂O₂(O₂)₄F]·2H₂O, respectively, complexes of two new types have been obtained: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O(x0.25,3) and the first trinuclear peroxo complex of vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O(4).

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Tetraalkylammonium-Fluorooxoperoxovanadate

Zusammenfassung Aus dem SystemMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄), N(C₂H₅)₄, N(C₄H₉)₄) kristallisierende Verbindungen wurden mittels Elementaranalyse, Schwingungsspektroskopie und Röntgendiffraktion charakterisiert. Neben [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) und [N(CH₃)₄]₃][V₂O₂(O₂)₄F] (2), welche den bekannten VerbindungenM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) und (NH₄)₃[V₂O₂(O₂)₄)F]·2H₂O entsprechen, wurden zwei neue Typen von Komplexen erhalten: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O (x0.25,3) und der erste dreikernige Peroxokomplex von Vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O (4).

     

Propane‐1,3‐diaminium tetrachloridozincate(II) 18‐crown‐6 clathrate

The reaction of propane‐1,3‐diamine hydrochloride, 18‐crown‐6 and zinc(II) chloride in methanol solution yields the title complex salt [systematic name: propane‐1,3‐diaminium tetrachloridozincate(II)–1,4,7,10,13,16‐hexaoxacyclooctadecane (1/1)], (C₃H₁₂N₂)[ZnCl₄]·C₁₂H₂₄O₆, with an unusual supramolecular structure. The diprotonated propane‐1,3‐diaminium cation forms an unexpected 1:1 supramolecular rotator–stator complex with the crown ether, viz. [C₃H₁₂N₂(18‐crown‐6)]²⁺, in which one of the –NH₃⁺ substituents nests in the crown and interacts through N—H...O hydrogen bonding. The other –NH₃⁺ group interacts with the [ZnCl₄]²⁻ anion via N—H...Cl hydrogen bonding, forming cation–crown–anion ribbons parallel to [010].     

Mössbauer study on solid state photolysis of alkali tris(malonato)ferrates(III)

Solid state photolysis of alkali tris(malonato)ferrates(III), i.e., M₃[Fe(CH₂C₂O₄)₃]xH₂O (M=Li, Na, K, NH₄) has been studied employing Mössbauer, infrared and reflectance spectroscopic techniques. The complexes were irradiated for 300 hours using a medium pressure mercury vapour lamp of 250 W, Photodecomposition led to the formation of an iron(II) intermediate, M₂[Fe^II(CH₂C₂O₄)₂(H₂O)₂] (M=Li, Na, K) which on prolonged standing in air oxidized to M[Fe^III(CH₂C₂O₄)₂(H₂O)₂]. However, in case of ammonium complex, Fe^IICH₂C₂O₄·2H₂O once formed remained stable. The extent of photoreduction showed the sequence: NH₄, K>Li>Na. The results have been compared with those of alkali tris (oxalato) ferrates(III).     

Bis(iminodiethylenedi­ammonium) di‐μ5‐hydrogen­phosphato‐penta­molybdate(VI) tetra­hydrate

The crystal structure of the title compound, (C₄H₁₅N₃)₂[Mo₅O₁₅(HPO₄)₂]·4H₂O, is made up of [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters, iminodiethylenediammonium cations and solvent water mol­ecules. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster, with approximate C₂ symmetry, can be considered as a ring formed by five distorted edge‐ and corner‐sharing MoO₆ octa­hedra, capped on both poles by a hydro­phosphate tetra­hedron. There exist N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds between the organic ammonium groups and the clusters, with inter­atomic N⋯O distances ranging from 2.675 (3) to 2.999 (3) Å, and C⋯O distances ranging from 3.139 (5) to 3.460 (5) Å.     

Past,present and future of the clathrate inclusion compounds built of cyanometallate hosts

One-, two- and three-dimensional CN-bridged metal complex structures made up of building blocks such as linear [Ag(CN)₂]^–, square planar [Ni(CN)₄]^2– or tetrahedral [Cd(CN)₄]^2–, and of the complementary ligands such as ammonia, water, unidentate amine, bidentate a,w- diaminoalkane, etc., are reviewed with an emphasis on their behaviour as hosts to afford clathrate inclusion compounds with guest molecules and as self-assemblies to form supramolecular structures with or without guests. The historical background is explained for Prussian blue and Hofmann's benzene clathrate based on their single crystal structure determinations. The strategies the author and coworkers have been applying to develop varieties of clathrate inclusion compounds from the Hofmann-type are demonstrated with the features observed for the developed structures determined by single crystal X-ray diffraction methods.Abbreviations for Ligands and Guests mma NMeH₂ - dma NMe₂H - tma NMe₃ - mea NH₂(CH₂)₂OH - en NH₂(CH₂)₂NH₂ - pn NH₂CHMeCH₂NH₂ - tn NH₂(CH₂)₃NH₂ - dabtn NH₂(CH₂)₄NH₂ - daptn NH₂(CH₂)₅NH₂ - dahxn NH₂(CH₂)₆NH₂ - dahpn NH₂(CH₂)₇NH₂ - daotn NH₂(CH₂)₈NH₂ - danon NH₂(CH₂)₉NH₂ - dadcn NH₂(CH₂)₁₀NH₂ - mtn NMeH(CH₂)₃NH₂ - dmtn NMe₂(CH₂)₃NH₂ - detn NEt₂(CH₂)₃NH₂ - temtn NMe₂(CH₂)₃NMe₂ - dien NH₂(CH₂)₂NH(CH₂)₂NH₂ - pXdam p-C₆H₄(NH₂CH₂)₂ - rnXdam m-C₆H₄(NH₂CH₂)₂ - py C₅H₅N pyridine - ampy NH₂C₅H₄N aminopyridine - Clpy CIC₅H₄N chloropyridine - Mepy MeC₅H₄N methylpyridine - dmpy Me₂C₅H₃N dimethylpyridine - bpy NC₅H₄C₅H₄N bipyridine - quin C₇H₉N quinoline - iquin iso-C₇H₉N isoquinoline - qxln C₈H₆N₂ quinoxaline - Pe C₅H₁₁-pentyl imH: C₃N₂H₄ imidazole - pyrz N(CHCH)₂N pyrazine - Mequin MeC₇H₈N methylquinoline - bppn C₁₃H₁₄N₂ 1,3-bis(4-pyridyl)propane - bpb C₁₄H₈N₂ 1,4-bis(4-pyridyl)butadiyne - N-Meim C₃N₂H₃Me N-methylimidazole - 2-MeimH C₃N₂H₃Me 2-methylimidazole - dmf HOCNMe₂ dimethylformamide - hmta C₆H₁₂N₄ hexamethylenetetramine - o-phen C₁₂H₈N₂ 1,10-phenanthroline - den HN(CH₂CH₂)₂NH piperazine - morph HN(CH₂CH₂)₂O morpholine - ten N(CH₂CH₂)₃N 1,4-diazabicyclo[2.2.2]octane - ameden NH₂(CH₂)₂N(CH₂CH₂)₂NH N-(2-aminoethyl)piperazine Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Cationic Allyl Complexes of the Rare‐Earth Metals: Synthesis,Structural Characterization,and 1,3‐Butadiene Polymerization Catalysis

Monocationic bis‐allyl complexes [Ln(η³‐C₃H₅)₂(thf)₃]⁺[B(C₆X₅)₄]^? (Ln=Y, La, Nd; X=H, F) and dicationic mono‐allyl complexes of yttrium and the early lanthanides [Ln(η³‐C₃H₅)(thf)₆]²⁺[BPh₄]₂^? (Ln=La, Nd) were prepared by protonolysis of the tris‐allyl complexes [Ln(η³‐C₃H₅)₃(diox)] (Ln=Y, La, Ce, Pr, Nd, Sm; diox=1,4‐dioxane) isolated as a 1,4‐dioxane‐bridged dimer (Ln=Ce) or THF adducts [Ln(η³‐C₃H₅)₃(thf)₂] (Ln=Ce, Pr). Allyl abstraction from the neutral tris‐allyl complex by a Lewis acid, ER₃ (Al(CH₂SiMe₃)₃, BPh₃) gave the ion pair [Ln(η³‐C₃H₅)₂(thf)₃]⁺[ER₃(η¹‐CH₂CH?CH₂)]^? (Ln=Y, La; ER₃=Al(CH₂SiMe₃)₃, BPh₃). Benzophenone inserts into the La? C_allyl bond of [La(η³‐C₃H₅)₂(thf)₃]⁺[BPh₄]^? to form the alkoxy complex [La{OCPh₂(CH₂CH?CH₂)}₂(thf)₃]⁺[BPh₄]^?. The monocationic half‐sandwich complexes [Ln(η⁵‐C₅Me₄SiMe₃)(η³‐C₃H₅)(thf)₂]⁺[B(C₆X₅)₄]^? (Ln=Y, La; X=H, F) were synthesized from the neutral precursors [Ln(η⁵‐C₅Me₄SiMe₃)(η³‐C₃H₅)₂(thf)] by protonolysis. For 1,3‐butadiene polymerization catalysis, the yttrium‐based systems were more active than the corresponding lanthanum or neodymium homologues, giving polybutadiene with approximately 90 % 1,4‐cis stereoselectivity.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.     

Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.     

Two isomorphous ZnII/CoII complexes with tri‐tert‐butoxysilanethiol and histamine,and (4‐hydroxymethyl‐1H‐imidazole‐κN)bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II)

The complexes [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], and [2‐(1H‐imidazol‐4‐yl‐κN³)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₅H₉N₃)], are isomorphous. The central Zn^II/Co^II ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH₂ groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The Zn^II atom in [(1H‐imidazol‐4‐yl‐κN³)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ²O,S)zinc(II), [Zn(C₁₂H₂₇O₃SSi)₂(C₄H₆N₂O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.     

New Heterocyclic Organophosphorus–Sulfur–Nitrogen Compounds,Syntheses and Structures

The new compound C₁₀H₆P(S)[NSi(CH₃)₃]₂P(S) ( 3 ) which contains a P₂N₂ heterocycle has been prepared in low yield by partial thermal decomposition of 1-{[N,N′-bis(trimethylsilyl)acetamidinium]sulfido}-3-(trimethylsilylamino)-1 H,3 H,1 λ⁵,3 λ⁵-naphtho[1,8 a,8-cd][1,2,6]thiadiphosphinine-1,3-dithione [CH₃C{NHSi(CH₃)₃}₂]⁺[C₁₀H₆P(S)(NHSiMe₃)SP(S)₂]^– ( 2 ). Reaction of 2 with potassium hydroxide in acetonitrile gives the completely desilylated product [CH₃C(NH₂)₂]⁺[C₁₀H₆P(S)(NH₂)SP(S)₂]^– ( 4 ). The structures of the new compounds 3 and 4 were elucidated by FTIR and NMR spectroscopy methods and by X-ray structure analyses.     

An ion pair uniting a gadolinium(III)–Schiff base complex and uranyl tetrachloride

The Schiff base N‐(tert‐butyl)‐3‐methoxy­salicyl­ald­imine (LH) forms a complex with gadolinium(III) chloride, [GdCl₂(LH)₂(C₅H₅N)₂]⁺, in which the two O atoms of each ligand are coordinated (the phenolic O atom being deprotonated) and the imine N atom is protonated and involved in a hydrogen bond with the phenoxide group. This complex crystallizes as an ion pair with uranyl tetrachloride, i.e. bis{bis­[2‐(tert‐butyl­iminio­methyl)‐6‐methoxy­phenolato‐O,O′]­dichlorobis­(pyridine‐N)­gadolinium(III)} tetra­chlorodi­oxo­uran­ium(VI) tetra­pyri­dine solvate [GdCl₂(C₁₂H₁₇NO₂)₂(C₅H₅N)₂]₂[UCl₄O₂]·4C₅H₅N. The U atom of the UCl₄O₂ anion lies on an inversion centre.     

catena‐Poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ2N,N′)copper(II)]‐μ‐di­thion­ato‐κ2O:O′] and trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ2N,N′)copper(II) di­thionate

In title an­hydro­us catena‐poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ²N,N′)copper(II)]‐μ‐di­thionato‐κ²O:O′], [Cu(S₂O₆)(C₂H₈N₂)₂]_n or [{H₂N(CH₂)₂NH₂}₂Cu(O·O₂SSO₂·O)]_∞, successive Cu atoms are bridged by a single doubly charged di­thionate group, forming a one‐dimensional polymer with inversion centres at the metal atoms and the mid‐point of the S—S bond [Cu—O = 2.5744 (15) Å]. In title (hydrated) trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ²N,N′)copper(II) di­thionate, [Cu(C₃H₁₀N₂)₂(H₂O)₂](S₂O₆) or [{H₂N(CH₂)₃NH₂}₂Cu(OH₂)₂](S₂O₆), both ions have imposed 2/m symmetry. The `axial' anion components are displaced by a pair of water ligands [Cu—O = 2.439 (3) Å], the shorter Cu—O distance being compensated by the lengthened Cu—N distance [2.0443 (18), cf. 2.0100 (13) and 2.0122 (16) Å].     

Molybdenum Bisphosphonates with Cr(III) or Mn(III) Ions

The synthesis of Mo^VI bisphosphonates (BPs) complexes in the presence of a heterometallic element has been studied. Two different BPs have been used, the alendronate ligand, [O₃PC(C₃H₆NH₃)(O)PO₃]^4? (Ale) and a new BP derivative with a pyridine ring linked to the amino group, [O₃PC(C₃H₆NH₂CH₂C₅H₄N)(O)PO₃]^4? (AlePy). Three compounds have been isolated, a tetranuclear Mo^VI complex with Cr^III ions, (NH₄)₅[(Mo₂O₆)₂(O₃PC(C₃H₆NH₃)(O)PO₃)₂Cr]·11H₂O (Mo₄(Ale)₂Cr), its Mn^III analogue, (NH₄)_4.5Na_0.5[(Mo₂O₆)₂(O₃PC(C₃H₆NH₃)(O)PO₃)₂Mn]·9H₂O (Mo₄(Ale)₂Mn), and a cocrystal of two polyoxomolybdates, (NH₄)₁₀Na₃[(Mo₂O₆)₂(O₃PC(C₃H₆NH₂CH₂C₅H₄N)(O)PO₃)₂Cr]₂[CrMo₆(OH)₆O₁₈]·37H₂O ([Mo₄(AlePy)₂Cr]₂[CrMo₆]). In this latter compound an Anderson-type POM [CrMo₆(OH)₆O₁₈]^3? is sandwiched between two tetranuclear Mo^VI complexes with AlePy ligands. The protonated triply bridging oxygen atoms bound to the central Cr^III ion of the Anderson anion develop strong hydrogen bonding interactions with the oxygen atoms of the bisphosphonate complexes. The UV–Vis spectra confirm the coexistence in solution of both POMs. Cyclic voltammetry experiments have been performed, showing the reduction of the Mo centers. In strong contrast with the reported Mo^VI BP systems, the presence of trivalent cations in close proximity to the Mo^VI centers dramatically impact the potential solid-state photochromic properties of these compounds.     

Template Syntheses of Copper(II) Complexes from Arylhydrazones of Malononitrile and their Catalytic Activity towards Alcohol Oxidations and the Nitroaldol Reaction: Hydrogen Bond‐Assisted Ligand Liberation and E/Z Isomerisation

A one‐pot template condensation of 2‐(2‐(dicyanomethylene)hydrazinyl)benzenesulfonic acid (H₂L¹, 1 ) or 2‐(2‐(dicyanomethylene)hydrazinyl)benzoic acid (H₂L², 2 ) with methanol (a), ethylenediamine (b), ethanol (c) or water (d) on copper(II), led to a variety of metal complexes, that is, mononuclear [Cu(H₂O)₂(κO¹,κN² L^1a] ( 3 ) and [Cu(H₂O)(κO¹,κN³ L^1b)] ( 4 ), tetranuclear [Cu₄(1 κO¹,κN²:2 κO¹ L^2a)₃‐(1 κO¹, κN²:2 κO² L^2a)] ( 5 ), [Cu₂(H₂O)(1 κO¹, κN²:2 κO¹ L^2c)‐(1 κO¹,1 κN²:2 κO¹,2 κN¹‐ L^2c)]₂ ( 6 ) and [Cu₂(H₂O)₂(κO¹,κN²‐ L^1dd)‐(1 κO¹,κN²:2 κO¹ L^1dd)(μ‐H₂O)]₂ ? 2 H₂O ( 7? 2 H₂O), as well as polymer‐ ic [Cu(H₂O)(κO¹,1 κN²:2 κN¹ L^1c)]_n ( 8 ) and [Cu(NH₂C₂H₅)(κO¹,1 κN²:2 κN¹L^2a)]_n ( 9 ). The ligands 2‐SO₃H‐C₆H₄‐(NH)N?C{(CN)[C(NH₂)‐(?NCH₂CH₂NH₂)]} (H₂L^1b, 10 ), 2‐CO₂H‐C₆H₄‐(NH)N?{C(CN)[C(OCH₃)‐(?NH)]} (H₂L^2a, 11 ) and 2‐SO₃H‐C₆H₄‐(NH)N?C{C(?O)‐(NH₂)}₂ (H₂L^1dd, 12 ) were easily liberated upon respective treatment of 4 , 5 and 7 with HCl, whereas the formation of cyclic zwitterionic amidine 2‐(SO₃^?)? C₆H₄? N?NC(? C?(NH⁺)CH₂CH₂NH)(?CNHCH₂CH₂NH) ( 13 ) was observed when 1 was treated with ethylenediamine. The hydrogen bond‐induced E/Z isomerization of the (HL^1d)^? ligand occurs upon conversion of [{Na(H₂O)₂(μ‐H₂O)₂}(HL^1d)]_n ( 14 ) to [Cu(H₂O)₆][HL^1d]₂ ? 2 H₂O ( 15 ) and [{CuNa(H₂O)‐(κN¹,1 κO²:2 κO¹ L^1d)₂}K_0.5(μ‐O)₂]n ? H₂O ( 16 ). The synthesized complexes 3 – 9 are catalyst precursors for both the selective oxidation of primary and secondary alcohols (to the corresponding carbonyl compounds) and the following diastereoselective nitroaldol (Henry) reaction, with typical yields of 80–99 %.