Über Tris(siloxymethyl)-, Tris(silylmercaptomethyl)- und Tris(silylmethyl)amine

By the reaction of alkali salts of triorgano-silanols, -silanethiols and trimethylsilylmethanol as well as of triorganosilyllithium compounds with tris(chloromethyl)amine, silyl derivatives of tris(hydroxymethyl)-, tris(mercaptomethyl)- and tris(methyl)amine were prepared.     

Two new [Ni(tren)2]2+ complexes: [Ni(tren)2]Cl2 and [Ni(tren)2]WS4

Both title compounds, bis­[tris(2‐amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2‐amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2‐amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS₄]^2? anion in (II). Hydro­gen bonding is observed in both compounds.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

Ruthenium‐catalyzed formation of quinolines via reductive cyclization of nitroarenes with tris(3‐hydroxypropyl)amine in an aqueous medium

Nitroarenes react with tris(3‐hydroxypropyl)amine in an aqueous medium (dioxane/H₂O) at 180° in the presence of a catalytic amount of a ruthenium catalyst and tin(II) chloride along with isopropanol as hydrogen donor to afford the corresponding quinolines in good yields. The presence of tin(II) chloride is essential for the formation of quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from tris(3‐hydroxypropyl)amine to anilines to form 3‐anilino‐1‐propanols, N‐alkylation of anilines by 3‐anilino‐1‐propanol to form 1,3‐dianilinopropane and intramolecular heteroannulation of 1,3‐dianilinopropane is proposed for this catalytic process.     

Solvothermal Synthesis and Characterization of the New Iron Thioantimonates(III) [Fe(C6H18N4)]FeSbS4 and [Fe(C4H13N3)2]Fe2Sb4S10 Containing FeII and FeIII and Protein‐Analogous [2FeIII‐2S]2+ Clusters

The two new compounds [Fe(tren)]FeSbS₄ ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)₂]Fe₂Sb₄S₁₀ ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe³⁺ is part of a [2Fe^III‐2S] cluster which is often found in ferredoxines. In addition, Fe²⁺ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe²⁺ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe²⁺ ion is isolated. In both compounds the primary SbS₃ units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS₄ was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step.     

|(C6N4H21)2|[Ge7O14F6]: A New Germanate Compound Constructed from Alternately Stacked Pseudo Triple‐Sheet Layers

A novel layered germanate compound, |(C₆N₄H₂₁)₂|[Ge₇O₁₄F₆] (JU‐86, JU = Jilin University), was solvothermally synthesized. Its structure consists of 4.6‐net sheets built up from dissymmetric 8³ building units. Different from those found in several metal phosphate compounds, half of the 4.6‐net sheets in JU‐86 are constructed from right‐handed 8³ building units and the other half are constructed from left‐handed ones. Right‐handed and left‐handed 4.6‐net sheets are stacked alternately in JU‐86. Each 4.6‐net sheet is sandwiched by two layers of protonated tris(2‐aminoethyl)amine (tren) molecules to form an unusual pseudo triple‐sheet layer through hydrogen‐bonding interactions. No hydrogen bonds are found between different pseudo triple‐sheet layers.     

Tetraiodide von Tris(1,2‐ethandiamin)komplexen der Metalle Zink und Nickel

The isotypic compounds tris(1,2‐ethanedi­amine‐N,N′)­zinc(II) triiodide iodide, [Zn(C₂H₈N₂)₃](I₃)I, and tris(1,2‐ethanedi­amine‐N,N′)­nickel(II) triiodide iodide, [Ni(C₂H₈N₂)₃](I₃)I, contain the octahedral [M(en)₃]²⁺ cation, with M = Zn and Ni, in both enantiomeric forms, an essentially linear triiodide anion and an iodide anion. The geometries of the complex ions are as expected, e.g.d(Ni—N) = 2.123 (5), 2.127 (6) and 2.134 (5) Å, and d(Zn—N) = 2.176 (4), 2.193 (4) and 2.210 (4) Å. The shortest contact between the triiodide and iodide ions is 3.979 (1) Å for the nickel compound and 4.013 (1) Å for the zinc compound.     

A Study on Some Copper (II) Complexes of Polyaza Cryptands and Planar Macrocycles—Synthesis,Characterization and Superoxide Dismutase Activity

Two kinds of macrocyclic copper(II) complexes were synthesized. One of them is composed of copper(II) cryptates of ligands L¹‐L⁴ which are condensation products of 5‐R‐2‐methoxy‐1,3‐phenyldialdehyde (R=OCH₃, L¹) with tris(2‐aminoethyl) amine and 5‐R‐2‐methothoxy‐1, 3‐phenyldialdehyde (R= CH₃, L³) with tris(2‐aminopropyl)amine as well as their reduced products of L¹ and L³ (L² and L⁴). The other is composed of two‐dimensional macrocyclic copper(II) complexes of ligands L⁵‐L⁸ of condensation products of diethylene triamine with 4‐R‐l‐methoxy‐2,6‐phenyldialdehyde (R= Cl, Br. CH₃, OCH₃). The relationship between their structures and superoxide dismutase (SOD) activity was investigated. The results can provide some clues to the synthesis of SOD mimics.     

Furfuryl-containing tertiary phosphine oxides and polymers based on some of them

The syntheses of dimethyl(furfuryloxymethyl)phosphine oxide (DPO), methylbis(furfuryloxymethyl)phosphine oxide (MPO), tris(furfuryloxymethyl)phosphine oxide (TPO), dimethyl(tetrahydrofurfuryloxymethyl)phosphine oxide (DTPO), methyl-bis(tetrahydrofurfuryloxymethyl)phosphine oxide (MTPO) and tris(tetrahydrofurfuryloxymethyl)phosphine oxide (TTPO) from dimethyl(chloromethyl)phosphine oxide, methyl-bis(chloromethyl)phosphine oxide, tris(chloromethyl)phosphine oxide and the furfuryl and tetrahydrofurfuryl sodium alkoxides via the Williamson reaction are reported. Phosphorus-containing furan polymers with reduced flammability are prepared by polymerizing MPO and TPO using p-toluenesulphonic acid as catalyst. The oxygen indexes of these polymers, as determined by ASTM D-2863, are 35.1 and 33.1% O₂, respectively; for the phosphorus-free polymer from difurfurylidene acetone, it is 23.0% O₂. It is shown that DPO can be used as an efficient fire-retardant for reducing the flammability of a polymer from difurfurylidenacetone.     

A pseudo‐cage complex of silver(I) with tripodal tetraamine having benzyl end groups, {tris[2‐(benzylamino)ethyl]amine‐κ4N}silver(I) perchlorate

The synthesis and crystal structure of {tris­[2‐(benzyl­amino)­ethyl]­amine‐κ⁴N}silver(I) perchlorate, [Ag(C₂₇H₃₆N₄)]ClO₄ or [Ag(bz₃tren)]ClO₄ {bz₃tren is tris­[2‐(benzyl­amino)­ethyl]­amine or N,N′,N′′‐tri­benzyl­tris(2‐amino­ethyl)­amine} are reported. The Ag atom is coordinated to four N atoms of the tren unit and is located 0.604 (3) Å out of the trigonal plane described by the three secondary amine N atoms, away from the bridgehead N atom. Edge‐to‐face π–π interactions between the aromatic end groups, and weak interactions between Ag and arene, allow the formation of a pseudo‐cage complex.     

A Water‐Soluble Copper–Polypyridine Complex as a Homogeneous Catalyst for both Photo‐Induced and Electrocatalytic O2 Evolution

The water‐soluble polypyridine copper complex [Cu(F₃TPA)(ClO₄)₂] [ 1 ; F₃TPA=tris(2‐fluoro‐6‐pyridylmethyl)amine] catalyzes water oxidation in a pH 8.5 borate buffer at a relatively low overpotential of 610 mV. Assisted by photosensitizer and an electron acceptor, 1 also exhibits activity as a homogeneous catalyst for photo‐induced O₂ evolution with a maximum turnover frequency (TOF) of (1.58±0.03)×10^?1 s^?1 and a maximum turnover number (TON) of 11.61±0.23. In comparison, the reference [Cu(TPA)(ClO₄)₂] [TPA=tris(2‐pyridylmethyl)amine] displayed almost no activity under either set of conditions, implying the crucial role of the ligand in determining the behavior of the catalyst. Experimental evidence indicate the molecular catalytic nature of 1 , leading to a potentially practical strategy to apply the copper complex in a photoelectrochemical device for water oxidation.     

Strong Direct Magnetic Coupling in a Dinuclear CoII Tetrazine Radical Single‐Molecule Magnet

The ligand‐centered radical complex [(CoTPMA)₂‐μ‐bmtz^.?](O₃SCF₃)₃ ? CH₃CN (bmtz=3,6‐bis(2′‐pyrimidyl)‐1,2,4,5‐tetrazine, TPMA=tris‐(2‐pyridylmethyl)amine) has been synthesized from the neutral bmtz precursor. Single‐crystal X‐ray diffraction studies have confirmed the presence of the ligand‐centered radical. The Co^II complex exhibits slow paramagnetic relaxation in an applied DC field with a barrier to spin reversal of 39 K. This behavior is a result of strong antiferromagnetic metal–radical coupling combined with positive axial and strong rhombic anisotropic contributions from the Co^II ions.     

“Off‐on‐off” Fluorescence pH Switch of Three Trinuclear RuII Complexes Containing Imidazole Rings

Three tripodal ligands H₃L^1–3 containing imidazole rings were synthesized by the reaction of 1,10‐phenanthroline‐5,6‐dione with 1,3,5‐tris[(3‐formylphenoxy)methyl]benzene, 1,3,5‐tris[(3‐formylphenoxy)methyl]‐2,4,6‐trimethylbenzene, and 2,2′,2"‐tris[(3‐formylphenoxy)ethyl]amine, respectively. Trinuclear Ru^II polypyridyl complexes [(bpy)₆Ru₃H₃L^1–3](PF₆)₆ were prepared by the condensation of Ru(bpy)₂Cl₂ · 2H₂O with ligands H₃L^1–3. The pH effects on the UV/Vis absorption and fluorescence spectra of the three complexes were studied, and ground‐ and excited‐state ionization constants of the three complexes were derived. The three complexes act as “off‐on‐off” fluorescence pH switch through protonation and deprotonation of imidazole ring with a maximum on‐off ratio of 5 in buffer solution at room temperature.     

Two transition metal coordination polymers of the 7,7,8,8‐tetracyanoquinodimethane dianion (TCNQ2−)

Each of the two novel title transition metal coordination polymers, namely catena‐poly[[bis{[tris(2‐pyridylmethyl)amine]cobalt(II)}‐μ₄‐7,7,8,8‐tetracyanoquinodimethanide(2−)] bis[7,7,8,8‐tetracyanoquinodimethanide(1−)] methanol disolvate], {[Co₂(C₁₂H₄N₄)(C₁₈H₁₈N₄)₂](C₁₂H₄N₄)₂·2CH₃OH}_n, (I), and catena‐poly[[[[tris(2‐pyridylmethyl)amine]iron(II)]‐μ₂‐7,7,8,8‐tetracyanoquinodimethanide(2−)] methanol solvate], {[Fe(C₁₂H₄N₄)(C₁₈H₁₈N₄)]·CH₃OH}_n, (II), contains η⁴‐TPA and cis‐bridging TCNQ²⁻ ligands [TPA is tris(2‐pyridylmethyl)amine and TCNQ is 7,7,8,8‐tetracyanoquinodimethane], but the two compounds adopt entirely different structural motifs. Compound (I) consists of a ribbon coordination polymer featuring μ₄‐TCNQ²⁻ radical anion ligands bridging four different octahedral Co^II centers. Each formula unit of the polymer is flanked by two uncoordinated TCNQ⁻ anions and two methanol solvent molecules. All three TCNQ anions have crystallographic inversion symmetry. In (II), the 2₁ symmetry operator generates a one‐dimensional zigzag chain of octahedral Fe^II centers with μ₂‐TCNQ²⁻ bridges. A methanol solvent molecule forms hydrogen bonds to one of the terminal N atoms of the bridging TCNQ²⁻ dianion. To the best of our knowledge, these are the first examples of one‐dimensional coordination polymers forming from cis coordination of two TCNQ ligands to octahedral metal centers.     

Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization

The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4‐(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP‐Cl, Cl‐I) was prepared via one‐step self‐assembly. SR&NI ATRP of styrene was conducted using CuCl₂ complex tris(2‐(dimethylamino)ethyl)amine (Me₆‐TREN) as the catalytic system, initiated by 2,2‐azobis(isobutyronitrile) (AIBN) and ATP‐Cl. FT‐IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl₂. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2～1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1508–1516     

The new thioantimonate(V) (C3H10N)[NiSbS4(C6H18N4)]

Turquoise crystals of the title salt, propyl­ammonium di‐μ‐thio‐1:2κ⁴S‐di­thio‐2κ²S‐tris(2‐amino­ethyl)­amine‐1κ⁴N‐anti­mony(V)­nickel(II), (C₃H₁₀N)[NiSbS₄(C₆H₁₈N₄)] or [PAH][Ni(tren)SbS₄] [where tren is tris(2‐amino­ethyl)­amine and PA is propyl­amine], were synthesized under solvothermal conditions by reacting [Ni(tren)₂]Cl₂, Sb and S in a solution of PA. The Ni^II ion is octahedrally surrounded by four N atoms of the tetradentate tren mol­ecule and by two S atoms of the tetrahedral [Sb^VS₄]^3? anion, thus forming the anionic [Ni(tren)SbS₄]^? part of the compound. Charge balance is achieved through the PAH⁺ cation. An extended intermolecular hydrogen‐bonding network is observed between the anion and the cation.     

Structures and Properties of Novel Mononuclear Iron(III) Complexes with Benzimidazole Containing Tripodal Tetradentate Ligands

The iron(III) complexes of the tripodal benzimidazole‐containing ligands tris(2‐benzimidazolylmethyl)amine (ntb), bis(2‐benzimidazolylmethyl)(2‐hydroxyethyl)‐amine (bbimae) and tris(5,6‐dimethyl‐2‐benzimidazolylmethyl)amine (me₂ntb) are structural and functional models for intradiol cleaving catechol dioxygenases. The complexes [Fe(ntb)Cl₂]Cl · 3 CH₃OH ( 1 ; P 1, a = 9.830(2) Å, b = 12.542(3) Å, c = 13.139(3) Å, α = 82.88(3)°, β = 73.45(3)°, γ = 85.53(3)°, V = 1539.2(6) ų; Z = 2) and [Fe(bbimae)Cl₂]Cl ( 2 ; P2₁/n, a = 7.461(2) Å, b = 18.994(5) Å, c = 14.515(4) Å, β = 98.22(2)°, V = 2035.8(9) ų, Z = 4) have been characterized by X‐ray crystallography and spectroscopic methods. In the octahedrally coordinated complexes two cis coordination sites – essential for catechol binding – are occupied by chloride ligands. The significant intradiol cleaving catechol dioxygenase activity of the model complexes was examined using 3,5‐di‐tert‐butylcatechol as a substrate.     

Tris(dialkylamino)benzylphosphoniumbromide – Phosphoniumsalze mit drei nahezu planar konfigurierten N‐Atomen

Tris(dialkylamino)benzylphosphonium Bromides – Phosphonium Salts with three N Atoms configurated nearly planar Tris(dialkylamino)benzylphosphonium bromides [(R₂N)₃PCH₂C₆H₅]⁺Br^– (R: Me, Et, n‐Pr, n‐Bu) have been obtained by the reaction of the corresponding tris(dialkylamino)phosphines with benzylbromide in good yields. The compounds crystallize as colorless solids from acetonitrile or methylene chloride after addition of diethylether. The corresponding tris(dialkylamino)‐benzylphosphonium tribromides have been prepared by treating of the simple bromides with equimolar quantities of elemental bromine. The orange‐red precipitates have been recrystallized from the same solvents by addition of diethylether. In all compounds investigated the crystal structure analyses showing three N atoms with a nearly planar configuration.