Mono‐ and Dinuclear Ferrocenyl Ionic Compounds with Polycyano Anions. Characterization,Migration, and Catalytic Effects on Thermal Decomposition of Energetic Compounds

Neutral ferrocene‐based burning rate (BR) catalysts show strong migration trends and volatility during long‐time storage and curing of the composite solid propellants. To reduce these disadvantages thirty‐two ferrocenyl quaternary ammonium compounds, paired with polycyano anions, were synthesized and characterized by ¹H NMR, ¹³C NMR, and UV/Vis spectroscopy, as well as elemental analysis. Additionally, crystal structures of eight compounds were confirmed by single‐crystal X‐ray diffraction. TG and DSC analyses indicated that the compounds containing 1,1,2,3,3‐pentacyanopropenide anions show high thermal stability. Cyclic voltammetry studies suggested that they are quasi‐reversible or irreversible redox systems. Anti‐migration tests verified that the tested compounds show very low migration tendency and some of them exhibit no migration after 30 days aging at 70 °C. Their catalytic efficiency in the thermal decomposition of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were examined by DSC analyses. The results revealed that most of the compounds exhibit distinct effects on the thermal degradation of AP and RDX. Two compounds have good catalytic ability in the thermal decomposition of HMX, representing rare examples of the reported ferrocenyl ionic compounds, which display catalytic property during combustion of HMX.     

Ferrocenyl Ionic Compounds Based on 5‐Ferrocenyl‐1H‐tetrazole. Synthesis,Characterization, Migration,and Catalytic Effects During Combustion

Ferrocenyl ionic compounds, consisting of the 5‐ferrocenyltetrazolate anion and a guanidinium or a 1‐alkyl‐3‐methylimidazolium cation, were synthesized and characterized by ¹H NMR, ¹³C NMR, and UV/Vis spectroscopy, as well as elementary analysis. The molecular structures of four compounds were additionally confirmed by single‐crystal X‐ray diffraction. Results of the TG and DSC analyses showed that some compounds display high thermal stability. Cyclic voltammetry investigations suggested that the compounds exhibit redox waves for the ferrocenyl groups and are considered as irreversible redox systems. Migration studies revealed that migration trends of the compounds are much lower than that of 2, 2‐bis(ethylferrocenyl)propane (Catocene), extensively used in composite solid propellants. Their catalytic performances for thermal decomposition of ammonium perchlorate (AP), 1, 3,5‐trinitro‐1, 3,5‐triazacyclohexane (RDX), and 1, 2,5, 7‐tetranitro‐1, 3,5, 7‐tetraazacyclooctane (HMX) were evaluated by DSC and/or TG techniques. Most of the compounds exhibit high catalytic efficiency in the thermal degradation of AP and RDX. Those of the guanidine‐containing compounds 1 – 3 are better, implying that nitrogen‐rich moieties are beneficial to enhancing released heats of some energetic materials. These guanidine salts could be used as ferrocene‐based burning rate catalyst candidates in composite solid propellants.     

Synthesis,Characterization and Migration of Ionic Polyferrocenyl Compounds of 5‐Ferrocenyl‐1H‐tetrazole and Their Effects During Combustion

Eighteen ionic polyferrocenyl compounds with 5‐ferrocenyl‐1H‐tetrazolate as anion and mono‐ and dinuclear ferrocenyl‐alkylammonium as cations were synthesized and characterized by ¹H NMR, ¹³C NMR, FT‐IR, and UV/Vis spectroscopy, and elemental analysis. Molecular structures of three compounds were further confirmed by single‐crystal X‐ray diffraction. Their thermal stability was evaluated by TG and DSC and found that they are of high thermal stability. The cyclic voltammetry analysis suggested that each of the compounds exhibits only an irreversible redox wave of the ferrocene units in the molecule. Both migration and volatility test results showed that, on comparison with those of Catocene, all tested compounds exhibit much more excellent anti‐migration ability and most of the tested compounds have lower volatility. Their effects on the thermal disintegration of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were measured by DSC. The results revealed that most of the compounds exhibit significant catalytic effects on the thermal degradation of AP and RDX. Particularly, most of the compounds containing one ferrocene unit in their cations show higher activity than that of Catocene. These compounds can be used as alternatives to Catocene in the composite solid propellants.     

Ferrocenyl Ionic Compounds Containing [Fe(CN)6]3– Anions: Synthesis,Characterization, and Catalytic Effects during Combustion

Twenty‐eight novel ferrocenyl ionic compounds, composed of mononuclear 1‐ferrocenylmethylalkyldimethylammoniums, 1‐ferrocenylmethyl‐3‐alkylimidazoliums, or their dinuclear analogs and [Fe(CN)₆]^3– anion, were designed and synthesized to tackle significant volatility and migration tendency of ferrocene‐based burning rate catalysts (BRCs) used currently in the composite solid propellants. The new compounds were characterized by UV/Vis, FT‐IR, and elementary analysis. The crystal structures of compounds 2· 5H₂O and 3· CH₂Cl₂ · 4H₂O verified the successful preparation of the desired ionic compounds. The TG tests at 70 °C for 24 h revealed that the new compounds exhibit lower volatility than catocene. The cyclic‐voltammetry results suggested that new compounds are quasi‐reversible or irreversible redox systems. TheTG/DSC analyses exhibited that the compounds are of highly thermal stability. Their catalytic effects on the thermal degradation of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazacyclooctane (HMX) were investigated. The results showed that most of the compounds exert great effects on the thermal degradation of AP and RDX during combustion. 11 and 2 are comparable to catocene in the thermal decomposition of AP and RDX, respectively, and can therefore be used as alternatives of catocene in a composite solid propellant. Some new compounds are unexpectedly active in promoting the thermal disintegration of HMX.     

“One‐Step” Synthesis of Ionic Ferrocenyl Compounds of Ferrocenylmethyldimethylamine. Characterization,Migration, and Catalytic Properties During Combustion

Alkylferrocene‐based burning rate catalysts exhibit high migration tendency and volatility during prolonged storage and fabrication process of the solid propellants. To retard the migration problems, eight ionic compounds composed of ferrocenylmethyldimethylammonium cation paired with a common energetic anion, were synthesized by “one‐step” procedure. The compounds were characterized by FT‐IR, NMR, and UV/Vis spectroscopy as well as elementary analysis. Their crystal structures were confirmed by single‐crystal X‐ray diffraction. The TG and DSC analyses indicated that they exhibit high thermal stability. Cyclic voltammetry studies suggested that most of them show reversible or quasi‐reversible redox waves. The anti‐migration results revealed that 1 – 4 are low‐migratory compounds, but 5 exhibits high migration trends. The TG curves at 70 °C for 24 h showed that all of them have low volatility. They have from high to low impact sensitivity depending on the anions of the compounds. They all exhibit significant effect on the thermal decomposition of ammonium perchlorate (AP) and some of them accelerate the thermal degradation of 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX). Among them 4 is the best one. Unexpectedly, compound 5 , with 1H‐tetrazolate as anion, can decompose into its original reactants at the temperature just higher than its melting point and could show smart‐material functionality in solid propellants.     

Synthesis and Characterization of a Dinuclear Nitrogen‐Rich Ferrocenyl Ligand and Its Ionic Coordination Compounds and Their Catalytic Effects During Combustion

Alkylferrocene‐based burning‐rate catalysts (BRCs) exhibit distinct migration tendency and high volatility and thus result in inferior performance of composite solid propellants during their combustion processes. To deal with these drawbacks, a novel dinuclear nitrogen‐rich ferrocene derivative, 4‐amino‐3,5‐bis(4‐ferrocenyl‐1,2,3‐triazolyl‐1‐methyl)‐1,2,4‐triazole (BFcTAZ) and its twenty seven ionic coordination compounds, [M₂(BFcTAZ)₂(H₂O)₄]_mX_n·xH₂O (M = Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Pb²; X = polycyano anions), were synthesized and characterized by FT‐IR, UV/Vis, and elementary analysis. Crystal structure of BFcTAZ was further confirmed by single‐crystal X‐ray diffraction and a general molecular structure of the new complexes was proposed. Their high thermal stability was verified by TG technique. Cyclic voltammetry studies suggested that the new compounds are diverse redox systems. Their effects on the thermal degradation of some common oxidizers were measured by DSC technique. The results indicated that most of the new complexes exert great effects on the thermal decomposition of AP, RDX, and 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and some of them are more active than catocene. The Cu²⁺ complexes are among the excellent ones. However, only six compounds have appreciable catalytic activity in the thermal degradation of HMX.     

Synthesis,Structure and Characterization of Dinuclear Pentacoordinate Molybdenum(V) Complexes with Thiosemicarbazone Ligands

New dinuclear pentacoordinate molybdenum(V) complexes, [Mo₂^VO₃L₂] [L = thiosemicarbazonato ligand: C₆H₄(O)CH:NN:C(S)NHR′ and C₁₀H₆(O)CH:NN:C(S)NHR′; R′ = H, CH₃, C₆H₅) were obtained either by oxygen atom abstraction from Mo^VIO₂L with triphenylphosphine or by using [Mo₂O₃(acac)₄] in the reaction with the corresponding ligands H₂L. Crystal and molecular structure of [Mo₂O₃{C₆H₄(O)CH:NN:C(S)NHC₆H₅}₂] · CH₃CN has been determined by the single‐crystal X‐ray diffraction method.     

A Dinuclear Ruthenium(II) Schiff Base Complex with Dissimilar Coordination: Synthesis,Characterization, and Biological Activity

A dinuclear Schiff base Ru^II complex derived from 5‐chlorosalicylaldehyde and 2‐aminopyridine was synthesized. The structure of the compound was analyzed by mass spectrometry as well as IR, UV/Vis, and ¹H NMR spectroscopy, along with chemical analysis,as well as magnetic, cyclovoltammetric and conductivity measurements. Two Ru^II atoms are octahedrally coordinated by azomethine and pyridine nitrogen atoms from two tridentate monobasic Schiff bases and bridging phenol oxygen atoms. The formula of the complex is [Ru₂L₂Cl₂(Et₂NH)(H₂O)] [L = N‐(2‐pyridyl)‐5‐chlorosalicylideneimine and Et₂NH = isodiethylamine]. The Ru^II atoms in the dinuclear neutral complex species have different coordination environments, RuN₃O₂Cl and RuN₂O₃Cl. Interaction with CT DNA showed moderate hydrophobic binding. The compound demonstrates strong activity against methicillin‐resistant Staphylococcus aureus, methicillin‐sensitive Staphylococcus aureus, and especially Enterococcus faecalis. Microbiological tests showed significant inhibition of growth and ability to kill pathogens, similar or even improved compared to reference antibiotics vancomycin.     

Synthesis and Structural Characterization of Dinuclear Oxorhenium(V) Complexes with Bidentate Imidazole Derivatives

The oxo-bridged dinuclear complexes [(μ-O){ReOCl₂(L)}₂] [L = 2-(1-ethylaminomethyl)-1-methylimidazole (eami); 2-(1-methylaminomethyl)-1-methylimidazole (mami); 2-(1-ethylthiomethyl)-1-methylimidazole (etmi)] were prepared by reaction of trans-[ReOCl₃(PPh₃)₂] with L in acetone. X-ray crystallographic studies of the eami and etmi complexes show that these ligands coordinate in a bidentate manner, and that the cis, cis-N₂Cl₂ and cis, cis-NSCl₂ equatorial planes are nearly orthogonal to the O=Re-O-Re=O backbone.     

Switching-On Fluorescence by Copper (II) and Basic Anions: A Case Study with a Pyrene-Functionalized Squaramide

The new symmetric acyclic N,N’-bis(1-pyrenyl) squaramide (H₂L) functionalized with the pyrene moiety as a fluorogenic fragment has been designed and its ability to selectively detect specific anions and metals investigated. H₂L selectively binds Cl⁻ both in solution (DMSO 0.5% H₂O and MeCN) and in the solid state, and allows to selectively detect Cu²⁺ in MeCN with the formation of a 2:1 metal-receptor complex, with a green intense emission appreciable by naked eye under the UV lamp. The H₂L copper complex preserves its emission properties in the presence of Cl⁻. The addition of basic anions (OH⁻, CN⁻, and F⁻) up to 10 equivalents caused the deprotonation of the squaramide NHs and a dramatic change of the emission properties of the H₂L copper complex.     

Reversible Uptake of COS,CS2, and SO2: Ionic Liquids with O‐Alkylxanthate,O‐Alkylthiocarbonyl,and O‐Alkylsulfite Anions

CO₂‐binding organic liquids (CO₂BOLs) are mixtures of a base (typically an amidine or guanidine) and an alcohol, and have been shown to reversibly capture and release CO₂ with low reaction energies and high gravimetric CO₂ capacity. We now report the ability of such liquid blends to chemically bind and release other acid gases such as CS₂, COS, and SO₂ analogously to CO₂. These systems bind with sulfur‐containing acid gases to form colored ionic liquids with new O‐alkylxanthate, O‐alkylthiocarbonyl, and O‐alkylsulfite anions. The capture and thermal stripping of each acid gas from these systems and their applicability towards flue gas desulfurization is discussed.     

具有不同类型桥基的双核Cu(Ⅱ)-Schiff碱配合物的合成和晶体结构

合成了３个分别以Ｃ２Ｏ２－４（［Ｃｕ２（Ｌ１）２（ｏｘ）］，１），ＡｃＯ－（［Ｃｕ２（ＡｃＯ）（Ｌ２）２］ＢＦ４，２）和酚氧（［Ｃｕ２（Ｌ３）２］（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物［Ｃｕ２（Ｌ１）２（ｏｘ）］·［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ（１′）及２和３的晶体结构．Ｘ射线衍射结果表明：１′，２和３分别属于Ｆｄｄｄ，Ｐ２１／ｃ和Ｐ２１／ｃ空间群．晶胞参数：［Ｃｕ２（Ｌ１）２（ｏｘ）］［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ，ａ＝２．４３９０（４）ｎｍ，ｂ＝３．０５３８（６）ｎｍ，ｃ＝１．８４９４（６）ｎｍ，α＝β＝γ＝９０．００°；２，ａ＝０．８４７（１）ｎｍ，ｂ＝２．６５４２（８）ｎｍ，ｃ＝１．４１００（６）ｎｍ，β＝９１．３４（６）°；３，ａ＝０．７６４６（３）ｎｍ，ｂ＝１．６９８３（３）ｎｍ，ｃ＝２．４４１７（３）ｎｍ，β＝９７．１１°     

Ionic Liquid Containing Copper(I): A New,Green, Homogeneous,and Reusable Catalyst for Click Cyclization

An ionic liquid containing copper(I) is introduced as a new, green, homogeneous, and reusable catalyst for click synthesis of 1,4-disubstituted-1H-1,2,3-triazoles from α-azido ketones and terminal alkynes in various solvents, especially in [bmim]BF₄. These cyclization reactions were efficiently performed in the presence of introduced ionic liquid catalyst with short reaction times and good yields. This catalytic ionic liquid exhibits excellent activity and can be simply recovered and reused for at least five runs without any loss in its activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Hydrothermal Synthesis, Crystal Structure, and Characterization of a Novel Terbium（Ⅲ） Coordination Polymer Bridged by 5-Sulfoisophthalate Trivalent Anions

Introduction Recently, several efforts have been made for thestudy of coordination polymers assembled from lantha-nide ions and aromatic polycarboxylate ligands becauseof their intriguing structural diversity and potentialapplications in several fields, s…     

Effect of Dimethyl Carbonate on the Dynamic Properties and Ionicities of Ionic Liquids with [MIII(hfip)4]− (M=B,Al) Anions

Several ionic liquids (ILs) comprising [B(hfip)₄]^? [hfip=OCH(CF₃)₂] or [Al(hfip)₄]^? anions and imidazolium or ammonium cations were prepared and mixed with up to 270 mol % of dimethyl carbonate (DMC). The viscosities, conductivities, and self‐diffusion constants of these mixtures and, where possible, of the neat ILs were measured and compared with common [NTf₂]^? based ILs and their mixtures with DMC. A tremendous decrease of the viscosities and a likewise increase of the conductivities and diffusion constants can be achieved for all classes of ILs. However, the order of the conductivities is partially reversed in the diffusion data. This is probably due to the low dielectric constant of DMC and the, thus, favored ion pairing, as evidenced, for example, by the calculated ionicities. Altogether, our data show that the chemically robust, but high‐melting and more viscous [B(hfip)₄]^? ILs might be candidates for electrolytes when mixed with suitable molecular solvents.     

Synthesis and Single Crystal Structure Characterization of Dinuclear and Polymeric Mixed-ligand Coordination Compounds of Zinc(II) and Cadmium(II) with the Bridging Ligand 1,2-Bis(pyridin-4-ylmethylene)hydrazine

Three d¹⁰-transition-metal coordination compounds [Cd(tfpb)₂(4-bpmh)]_n ( 1 ), [Cd(9-aca)(NO₃)(OHCH₃)(4-bpmh)]_n ( 2 ) and [Zn₂(dpp)₄(4-bpmh)] ( 3 ) with the bridging ligand 4-bpmh were synthesized [4-bpmh = 1,2-bis(pyridin-4-ylmethylene)hydrazine, tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate, 9-aca = anthracene-9-carboxylate, dpp = 1,3-diphenylpropane-1,3-dionate]. Compounds 1 – 3 were characterized by FT-IR spectroscopy, elemental analysis, and structurally authenticated by X-ray crystallography. Compounds 1 – 3 are constructed by an O,O'-donor ligand including chelating β-diketonates (tfpb, dpp) in 1 and 3 and a carboxylate ligand (9-aca) in 2 in combination with a linear neutral bidentate and bridging N-ligand (4-bpmh). The assembly and action of the bridging 4-bpmh ligand leads to one-dimensional coordination polymers in 1 , 2 and to a dinuclear coordination complex in 3 . The structures and the solid-state supramolecular interactions for studying the crystal packing fashions of 1 – 3 were analyzed. The supramolecular interactions including hydrogen bonding, C–H ··· π, π ··· π, and C–F ··· π in 1 , 2 , and 3 were founded.     

具有表面活性的功能化离子液体N-(三甲氧硅丙基)-N-甲基-2-吡咯烷酮盐酸盐的合成与表征

以N-甲基-2-吡咯烷酮和3-氯丙基三甲氧基硅烷单体为原料,利用SN2亲核取代反应合成具有一定表面活性的功能化离子液体N-(三甲氧硅丙基)-N-甲基-2-吡咯烷酮盐酸盐.通过元素分析、红外光谱和核磁共振对功能化离子液体进行表征,并测定了其表面张力和导电率.结果表明,合成的产物结构与其理论结构基本一致,具有较宽的液体温度范围和较低的表面张力,并具有较高的电导率,随着温度的升高,电导率逐渐增高.     

Cation and anion coordination chemistry of palladium(II) with polyazacycloalkanes. Thermodynamic and structural studies

The interaction of PdCl ₄ ^2– with the macrocyclic ligands of the series [3k]aneN _k has been studied both in solution and in the solid state. [18]aneN₆ and [21]aneN₇ form both mono- and binuclear Pd²⁺ complexes, whose stability constants have been determined in 0.5 mol dm^–3 NaCl at 298.15 K. [21]aneN₇ also forms, in solution, a trinuclear species in which an amino group deprotonates to bridge two Pd²⁺ ions, as observed in the solid state. The crystal structure of the complexes [Pd₂([18]aneN₆)Cl₂][ClO₄]₂ and [Pd₃([21]aneN₇)Cl₃][ClO₄]₂ · H₂O have been solved by single crystal X-ray analysis. C₁₂H₃₀N₆Cl₄O₈Pd₂: monoclinic, space group C2/m,a = 10.876(2),b = 18.117(2),c = 7.043(2) Å, = 113.78(2)°,V = 1270(12) ų,Z = 2,D _calc = 1.92 g cm^-3, = 16.94 cm^–1.R = 0.063,R _w = 0.059. C₁₄H₃₆N₇CI₅O₉Pd₃: orthorhombic, space groupPcab,a = 13.125(7),b = 13.213(3),c = 33.570(5) Å,V = 5822(3) ų,Z = 8,D _calc = 2.15 g cm^–3, = 21.20 cm^–1.R = 0.074,R _w = 0.061. In very acidic solutions the polyammonium cations (H _k [3k]aneN _k ) ^k+ interact with PdCl ₄ ^2– forming second sphere coordinated species. These reactions have been followed by a microcalorimetric technique in 2 mol dm^–3 HCl solutions. The slowness of the reactions of (H₁₀[30]aneN₁₀)¹⁰⁺ with PdCl ₄ ^2– has been interpreted in terms of inclusion of the anion into the receptor's cavity as shown by the crystal structure of [(PdCl₄)(H₁₀[30]aneN₁₀)][PdCl₄]₂Cl₄: triclinic, space group PT,a = 7.760(3),b = 11.448(4),c = 13.399(11) Å, = 96.31(8)°, = 104.50(6)°, = 92.30(3)°,Z = 1.R = 0.046 andR _w = 0.039.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

烷氧桥联混合配位的双核铜配合物的合成、结构及量子化学计算

0IntroductionThere has been intensive interests in the past fewyears for planar Cu-(μ-OR)-Cu dinuclear systems inwhichμ-OR=OH-,MeO-,EtO-[1￣5],especially for themagnetic behavior of planar[N2Cu(μ-OH)]systemsand the magneto-structural correlation between theangle Cu-O-Cu and the magnetical exchange parame-ter J[6,7].Some hydroxo-bridged Cu!compounds alsohave catalytic activity[8].In addition,low-molecular-weight Cu!coordination compounds with nitrogen-containing donors have frequent…