Hexanuclear Co4Dy2, Zn4Dy2, and Co4Y2 Complexes with Defect Tetracubane Cores: Syntheses,Structures, and Magnetic Properties

A hexanuclear heterometallic cluster of composition [Dy₂Co₄(L)₄(NO₃)₂(OH)₄(C₂H₅OH)₂] ⋅ 2 C₂H₅OH ( 1 ) was synthesized by employing a Schiff base 2-(((2-hydroxy-3-methoxybenzyl) imino)methyl)-4-methoxyphenol (H₂L) as ligand and utilizing Dy(NO₃)₃ ⋅ 6H₂O and Co(NO₃)₂ ⋅ 6H₂O as metal ion sources. X-ray single-crystal diffraction analysis indicated that complex 1 contains a defect tetracubane core and possesses central symmetric structure, with two Dy^III ions being in the central body position of the molecule and four Co^II ions being arranged at the outer sites. Magnetic studies reveal that complex 1 behaves as single-molecule magnet (SMM) with energy barrier of 27.50 K. To investigate the individual contribution of Dy^III and Co^II ions to the SMM behavior, another two complexes of formulae [Dy₂Zn₄(L)₄(NO₃)₂(OH)₄] ⋅ 4CH₃OH ( 2 ) and [Y₂Co₄(L)₄(NO₃)₂(OH)₄(C₂H₅OH)₂] ⋅ 2 C₂H₅OH ( 3 ) were prepared. Complexes 1 and 3 are isomorphous. The coordination geometries of Dy^III ions in 1 and 2 are different. The Dy^III ions are eight-coordinated in 2 and nine-coordinated in 1 . Complex 2 exhibits SMM behavior with energy barrier of 69.67 K, but complex 3 does not display SMM property. These results reveal that the SMM behaviors of 1 and 2 are mainly originated from Dy^III ions. It might be the higher symmetry of Dy^III ions in 2 that results in the higher energy barrier.     

Über sechsgliedrige Heterocyclen mit Phosphor-, Stickstoff- und Schwefelatomen im Ring

Cyclic sulphurylphosphazochloride (I: formula see ?Inhaltsübersicht”?) reacts with ammonia or methylamine forming the. tetramide(II) and (III), respectively, and with aniline or dimethylamine forming the diamide (IV) resp. (V). The synthesis of the diphenyl derivative (VI) is achieved starting from C₆H₅? PCl₄. (II) gives with PCl₅ the ionic compound (VII).     

The 13C NMR spectra,isomerism, and conformational analysis of substituted piperidin-4-ones

The ¹³C NMR spectra of 15 stereoisomers of 1-mono-, 1,2-di-, and 1,2,5-trisubstituted piperidin-4-ones were investigated, and the stereochemical orientations of the substituents and the conformation relationships were established. For the series of piperidones a method for determination of the absolute confirmation of the C₍₂₎ center of the piperidone ring is proposed on the basis of the chemical shifts of the methyl groups in the 1-s--phenylethyl substituent at the nitrogen atom in the preferred rotamers with respect to the C₍₁₎-N bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1503–1515, November, 1986.     

A ferrocenyl‐substituted pseudo­titanocene complex

The title compound, (η⁵‐cyclo­penta­dienyl)[(1,2,3,4,5‐η)‐4‐ferro­cenyl‐1,2,5,6‐tetrakis­(tri­methyl­silyl)­cyclo­hexa‐2,4‐dien‐1‐yl]­titanium(II), [TiFe(C₅H₅)₂(C₂₃H₄₂Si₄)] or [Ti{η⁵‐C₆H₂{Fe­(η⁵‐C₅H₄)(η⁵‐C₅H₅)}{Si(CH₃)₃}₄}(η⁵‐C₅H₅)], possesses two directly linked metallocene units that subtend an angle of 52.9 (1)° (defined by the least‐squares planes of the directly connected π‐ligands) associated with the steric requirements of the bulky tri­methyl­silyl substituents. The cyclo­hexa­dienyl ligand adopts an envelope conformation; the perpendicular distance of its η⁵‐plane to the Ti atom is 1.512 (1) Å.     

Polybromoaromatic Compounds: X. Reactions of Polybromobenzenes with Primary and Secondary Amines

Polybromobenzenes C₆Br₅X (X = Br, F, CN, NO₂) react with primary amines (methylamine and cyclohexylamine) to give nucleophilic substitution products; reactions of the same substrates with secondary amines (dimethylamine, diethylamine, piperidine, and morpholine) are accompanied by hydrodebromination processes.     

The nature of the [C2H6N]+ and [CH4N]+ ions formed by electron impact on methylated formamides,acetamides, ureas,thioureas and hexamethylphosphoramide

By means of appearance potential measurements and metastable analysis, it is shown that the [C₂H₆N]⁺ and [CH₄N]⁺ ions formed from methylated formamides, acetamides, ureas and thioureas rearrange upon formation to structures similar to the [M? H]⁺ ions from mono- and dimethylamine.     

Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phosphines

The derivatives of the H₂RuOs₃(CO)₁₃ and H₄Ru₄(CO)₁₂ carbonylhydride clusters containing functionalized (including chiral) phosphines were synthesized. The solid-state structure of H₂RuOs₃(CO)₁₂(Ph₂P(C₄H₃S)) was determined by X-ray diffraction analysis. The structures of other compounds in solution were determined using IR and ¹H and ³¹P NMR spectroscopy. A study of the temperature dependences of the ¹H NMR spectra of the phosphine-substituted tetrahedral clusters along with the analysis of literature data for their analogs showed that compounds of this type exist in solution as an equilibrium mixture of isomers, which differ in arrangement of the hydride ligands at the cluster skeleton. Interconversion of the isomeric forms is due to migration of the hydride ligands over the cluster skeleton. A general model for this dynamic process was proposed. The model is consistent with both our data and earlier results of other authors. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1294–1301, July, 2007.     

Synthesis and Properties of Complexes with Unusual {MnIII4} and {MnII4} Cages

Two types of manganese complexes with [Mn₄] cores featuring the unusual distorted cube topology are presented, the first of which comprises new modifications of the reported complex [Mn^III₄(sao)₄(saoH)₄]·3CHCl₃: [Mn₄(sao)₄(saoH)₄]·1.32(C₄H₁₀O)·0.43(CH₄O) ( 1a ) and [Mn(sao)₄(saoH)₄]·0.5(CH₄O)·0.5(C₂H₃N) ( 1b ) sao = salicylaldoxime. The second, 0.55[Mn₄Cl₄(C₁₂H₉N₂O)₄(CH₃OH)₂(H₂O)₂]·0.45[Mn₄Cl₄(C₁₂H₉N₂O)₄(CH₃OH)₄] ( 2 ), is the first reported case of a {Mn^II₄} core of this topology besides known {Mn^III₄} compounds. Differences between the {Mn^II₄} and {Mn^III₄} situation are discussed, and so far overlooked differences in magnetic properties between different {Mn^III₄} compounds are pointed out.     

Synthesis,characterization and biological studies of alkenyl‐substituted titanocene(IV) carboxylate complexes

The carboxylate compounds [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})(O₂CCH₂SXyl)₂] (2; Xyl = 3,5‐Me₂C₆H₃) and [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})(O₂CCH₂SMesl)₂] (3; Mes 1 = 2,4,6‐Me₃C₆H₂) were synthesized by the reaction of [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})Cl₂] (1) with 2 equivalents of xylylthioacetic acid or mesitylthioacetic acid, respectively. Compounds 2 and 3 were characterized by spectroscopic methods. The cytotoxic activity of 1–3 was tested against human tumor cell lines from four different histogenic origins—8505C (anaplastic thyroid cancer), DLD‐1 (colon cancer) and the cisplatin sensitive A253 (head and neck cancer) and A549 (lung carcinoma)—and compared with those of the reference complex [Ti(η⁵‐C₅H₅)₂Cl₂] (R1) and cisplatin. Surprisingly, the cytotoxic activities of the carboxylate derivatives were lower than those of their corresponding dichloride analogue (1). However, complexes 1–3 were more active than titanocene dichloride against all the studied cells with the exception of complex 2 against A253 and A549 cell lines. DNA‐interaction tests were also carried out. Solutions of all the studied complexes were treated with different concentrations of fish sperm DNA, observing modifications of the UV spectra with intrinsic binding constants of 2.99 × 10⁵, 2.45 × 10⁵, and 2.35 × 10⁵ M ^?1 for 1–3. Structural studies based on density functional theory calculations of 2 and 3 were also carried out. Copyright © 2010 John Wiley & Sons, Ltd.     

Ethyl and isopropyl 4‐ferrocenylbenzoate

The title compounds, [Fe(C₅H₅)(C₁₄H₁₃O₂)] and [Fe(C₅H₅)(C₁₅H₁₅O₂)], respectively, contain the ferrocenyl η⁵(C₅H₄) and phenyl­ene –C₆H₄– rings in a nearly coplanar arrangement, with interplanar angles of 6.88 (12) and 10.5 (2)°, respectively. Molecules of the ethyl ester form dimers through η⁵(C₅H₅)C—H⋯O=C hydrogen bonds, with graph set R(20), and, together with Csp³—H⋯π(C₅H₅) interactions, generate a one‐dimensional column (irregular ladder). Molecules of the iso­propyl ester aggregate through η⁵(C₅H₅)C—H⋯π(C₆H₄) interactions.     

Ammonolysis of Glyoxal at the Air-Water Nanodroplet Interface

The reactions of glyoxal (CHO)₂) with amines in cloud processes contribute to the formation of brown carbon and oligomer particles in the atmosphere. However, their molecular mechanisms remain unknown. Herein, we investigate the ammonolysis mechanisms of glyoxal with amines at the air-water nanodroplet interface. We identified three and two distinct pathways for the ammonolysis of glyoxal with dimethylamine and methylamine by using metadynamics simulations at the air-water nanodroplet interface, respectively. Notably, the stepwise pathways mediated by the water dimer for the reactions of glyoxal with dimethylamine and methylamine display the lowest free energy barriers of 3.6 and 4.9 kcal ⋅ mol⁻¹, respectively. These results showed that the air-water nanodroplet ammonolysis reactions of glyoxal with dimethylamine and methylamine were more feasible and occurred at faster rates than the corresponding gas phase ammonolysis, the OH+(CHO)₂ reaction, and the aqueous phase reaction of glyoxal, leading to the dominant removal of glyoxal. Our results provide new and important insight into the reactions between carbonyl compounds and amines, which are crucial in forming nitrogen-containing aerosol particles.     

Ion-Molecule reactions in methylamine and dimethylamine and trimethylamine systems

Fourier transform ion cyclotron resonance mass spectrometry has been used to measure the reaction rates for ions derived from methylamine with dimethylamine or trimethylamine. The use of the selective ion ejection technique greatly simplifies the elucidation of the ion-molecule reaction channels. The rate constants for proton transfer from protonated metwlamine, CH₃NH ₃ ⁺ (m/z 32), to dimethylamine and trimethylamine are 16.1 ± 1.6 × 10^?10 and 9.3 ± 0.9 × 10^?10 cm³ molec^?1s^?1, respectively. The rate constants for charge transfer from methylamine molecular ion, CH₃NH ₂ ⁺ (m/z 31), to dimethylamine and trimethylamine are 9.3 ± 1.8 x 10^?10 and 15.0 ± 5 × 10^?10 cm³molec^?1s^?1, respectively.     

Paddlewheel dirhodium complexes bridged by para‐substituted benzoates

The dirhodium complex bis­(benzonitrile)tetra­kis[μ‐4‐(diethyl­amino)benzoato‐κ²O:O′]dirhodium(II)(Rh—Rh) benzonitrile disolvate, [Rh₂(C₁₁H₁₄NO₂)₄(C₇H₅N)₂]·2C₇H₅N, lies about an inversion centre. The dirhodium complex (methanol)tetra­kis(μ‐4‐nitro­benzoato‐κ²O:O′)(pyridine)dirhodium(II)(Rh—Rh) dichloro­methane solvate, [Rh₂(C₇H₄NO₄)₄(C₅H₅N)(CH₄O)]·CH₂Cl₂, lies in a general position in the unit cell, but the complexes dimerize around an inversion centre via O—H⋯O hydrogen bonding of the axial MeOH to a carboxyl­ate O atom. In the latter crystal structure, π–π stacking inter­actions between the bridging 4‐nitro­benzoate ligands and the axial pyridine ligand are observed between adjacent mol­ecules.     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).     

Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

Derivatives of substituted 3‐trichlorogermylpropionic acid

The central Ge atoms in the structures of 3‐(2‐fluoro­phenyl)‐3‐(tri­phenyl­germyl)­propionic acid, [Ge(C₆H₅)₃(C₉H₈FO₂)], 3‐(2‐tolyl)‐3‐(tri‐4‐tolyl­germyl)­propionic acid, [Ge(C₇H₇)₃(C₁₀H₁₁O₂)], and 3‐(4‐tolyl)‐3‐(tri­benzyl­germyl)­propionic acid, [Ge(C₇H₇)₃(C₁₀H₁₁O₂)], are four‐coordinate with slightly distorted tetrahedral geometry. The Ge—Csp³ distances [1.970 (3)–1.997 (3) Å] are significantly longer than the Ge—C_aromatic distances [1.940 (3)–1.959 (2) Å]. In all three structures, the mol­ecules form dimeric pairs about inversion centres through strong hydrogen‐bonding interactions between carboxyl­ic acid groups.     

Organometallic Molybdenum(V) Complexes with Primary Phosphine Ligands. Syntheses,Spectroscopic Properties and Molecular Structures of [Cp°MoCl4(PH2R)] (R = But, 1‐Ad,Cy, Ph, 2, 4, 6‐Me3C6H2, 2, 4, 6‐Pri3C6H2, Cp° = C5EtMe4)

[Cp°MoCl₄] (Cp° = C₅EtMe₄) reacts with primary phosphines PH₂R to give the paramagnetic phosphine complexes [Cp°MoCl₄(PH₂R)] [Cp° = C₅EtMe₄, R = Bu^t ( 1 ), 1‐Ad (1‐Ad = 1‐adamantyl; 2 ), Cy ( 3 ), Ph ( 4 ), Mes (Mes = 2, 4, 6‐Me₃C₆H₂; 5 ), Tipp (Tipp = 2, 4, 6‐Prⁱ₃C₆H₂; 6 )]. 1 — 6 were characterized spectroscopically (IR, MS), and X‐ray crystal structures were determined for 1 — 4 and 6 . EPR investigations in liquid and frozen solution confirmed the presence of Mo^V species, and the data were used to analyze the spin‐density distribution in the first coordination sphere. Complexes 3 and 4 react with two equivalents of NEt₃ with formation of [Cp°MoCl₂(η³‐P₄Cy₄H)] ( 7 ) and [Cp°₂Mo₂(μ‐Cl)₂(μ‐P₄Ph₄)] ( 8 ), respectively, in low yield. Complexes 7 and 8 were characterized by X‐ray crystallography.     

Preparation and Reactivity of Mo(NCMe)(η2‐C2Ph2)2(η4‐C4Ph4)

Reaction of Mo(CO)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) and Me₃NO in acetonitrile solvent affords Mo(NCMe)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 1 . Compound 1 reacts with trimethylphosphine to produce Mo(PMe₃)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 2 , or reacts with diphenylacetylene to produce (η⁵‐C₅Ph₅)₂Mo 3 and Mo(η²‐O₂CPh)(η⁴‐C₄Ph₄H)(η⁴‐C₄Ph₄) 4 . The molecular structures of 1, 2 and 4 have been determined by an X‐ray diffraction study.     

[Mn(H2O)4(C4N2H4)][C6H4(COO)2] – Ein eindimensionales Koordinationspolymer mit kettenartigen [Mn(H2O)4(C4N2H4)]n2n+ Polykationen

[Mn(H₂O)₄(C₄N₂H₄)][C₆H₄(COO)₂] – An One‐Dimensional Coordination Polymer with Chain‐like [Mn(H₂O)₄(C₄N₂H₄)]_n²ⁿ⁺ Polycations Orthorhombic single crystals of [Mn(H₂O)₄(C₄N₂H₄)][C₆H₄(COO)₂] have been prepared in aqueous solution at room temperature. Space group Imm2 (no. 44), a = 1039.00(6) pm, b = 954.46(13) pm, c = 737.86(5) pm, V = 0.73172(12) nm³, Z = 2. Mn²⁺ is coordinated in a octahedral manner by four water molecules and two nitrogen atoms stemming from the pyrazine molecules (Mn–O 215.02(11) pm; Mn–N 228.7(4), 230.7(4) pm). Mn²⁺ and pyrazine molecules form chain‐like polycations with [Mn(H₂O)₄(C₄N₂H₄)]_n²ⁿ⁺ composition. The positive charge of the polycationic chains is compensated for by phthalate anions, which are accomodated between the chains. The phthalate anions are linked by hydrogen bonds to the polycationic chains. Thermogravimetric analysis in air revealed that the loss of water of crystallisation and pyrazine occurs in two steps between 130 and 245 °C. The resulting sample was stable up to 360 °C. Further decomposition yielded Mn₂O₃.     

Two derivatives of 1,5‐disubstituted tetrazoles: 1‐(4‐nitrophenyl)‐1H‐tetrazol‐5‐amine and {(E)‐[1‐(4‐ethoxyphenyl)‐1H‐tetrazol‐5‐yl]iminomethyl}dimethylamine

The geometric features of 1‐(4‐nitrophenyl)‐1H‐tetrazol‐5‐amine, C₇H₆N₆O₂, correspond to the presence of the essential interaction of the 5‐amino group lone pair with the π system of the tetrazole ring. Intermolecular N—H...N and N—H...O hydrogen bonds result in the formation of infinite chains running along the [110] direction and involve centrosymmetric ring structures with motifs R₂²(8) and R₂²(20). Molecules of {(E)‐[1‐(4‐ethoxyphenyl)‐1H‐tetrazol‐5‐yl]iminomethyl}dimethylamine, C₁₂H₁₆N₆O, are essentially flattened, which facilitates the formation of a conjugated system spanning the whole molecule. Conjugation in the azomethine N=C—N fragment results in practically the same length for the formal double and single bonds.