Synthesis and structure of heteroleptic triple-decker neodymium,europium, holmium,erbium, and ytterbium crown phthalocyaninates

Two series of heteroleptic crown-substituted tris(phthalocyaninate) complexes (Pc)Ln[(15C5)₄Pc]Ln(Pc) and [(15C5)₄Pc]Ln[(15C5)₄Pc]Ln(Pc), where 15C5 is 15-crown-5, (Pc²⁻) is the phthalocyaninate dianion, Ln = Nd, Eu, Ho, Er, and Yb, were prepared by the reaction of tetra-15-crown-5-phthalocyanine H₂[(15C5)₄Pc] with the corresponding lanthanide acetylacetonates and lanthanum bis(phthalocyaninate) La(Pc)₂, which was used as a phthalocyaninate dianion donor. The composition and structure of the synthesized complexes were confirmed by MALDI TOF mass spectrometry, UV-Vis absorption spectroscopy, and ¹H NMR. Complete assignment of the proton resonance signals of the paramagnetic lanthanide complexes was based on analysis of lanthanide-induced shifts.     

Syntheses and structures of Osmium(II) and Osmium(VI) <Emphasis Type="Italic">meso</Emphasis>-tetra(benzo-15-crown-5)porphyrinates according to the spectral data

The reaction of meso-tetra(benzo-15-crown-5)porphyrin (H₂TCP) with the osmium carbonyl complex Os₃(CO)₁₂ yieds the corresponding osmium(II) porphyrinate OsTCP(CO). The oxidation of OsTCP(CO) with air oxygen and hydrogen peroxide in neutral and acidic media was studied. A preparative method for the synthesis of osmium(VI) meso-tetra(benzo-15-crown-5)porphyrinate (OsO₂) TCP by the oxidation of OsTCP(CO) with 50% hydrogen peroxide in acetic acid was developed. The structures of new osmium porphyrinates were determined by IR, ¹H NMR, and UV/Vis spectroscopies.     

Palladium(II)-dppe-arylazoimidazole complexes: Synthesis,and spectroscopic characterization

Reaction of [Pd(dppe)Cl₂/Br₂] with AgOTf in a dichloromethane medium followed by ligand addition led to [Pd(dppe)(OSO₂CF₃)₂] and then [Pd(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p-R-C₆H₄-N=N-C₃H₂-NN-1-R′, (1–3), abbreviated as a N,N′-chelator, where N(imidazole) and N(azo) are represented by N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion, dppe = 1,2-bis-(diphenylphosphinoethane)]. ³¹P “¹H” NMR confirmed that due to the two phosphorus atom interaction in the azoimine symmetrical environment one sharp peak was formed. The ¹H NMR spectral measurements suggest that azo-imine link with lot of phenyl protons in the aromatic region. ¹³C (¹H) NMR spectrum, ¹H, ¹H COSY and ¹H, ¹³C HMQC spectrum assign the solution structure and stereo-retentive conformation in each complex.     

A novel series of nickel(II)-dppe-arylazoimidazole complexes. Synthesis and spectroscopic characterization

Reaction of [Ni(dppe)Cl₂/Br₂] with AgOTf in CH₂Cl₂ medium following ligand addition leads to [Ni(dppe)(OSO₂CF₃)₂] and then [Ni(dppe)(RaaiR)](OSO₂CF₃)₂ [RaaiR′ = p–R–C₆H₄–N=N–C₃H₂–NN-1–R′,(1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH₂CH₃ (2), CH₂Ph (3), OSO₂CF₃ is the triflate anion]. ³¹P{¹H}-NMR confirm that stable bis-chelated square planar Ni(II) azoimine–dppe complex formation with one sharp peaks. The ¹H NMR spectral measurements suggest azoimine link is present with lot of phenyl protons in the aromatic region. Considering all the moities there are a lot of different carbon atoms in the molecule which gives many different peaks in the ¹³C(¹H)-NMR spectrum. In the ¹H-¹H COSY spectrum in the present complexes and contour peaks in the ¹H-¹³C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive conformation in each complexes.     

Liquid Densities and Excess Molar Volumes for Binary Systems (Ionic Liquids + Methanol or Water) at 298.15, 303.15 and 313.15 K,and at Atmospheric Pressure

Binary excess molar volumes, V _m ^E, have been evaluated from density measurements, using a vibrating tube densimeter over the entire composition range for binary liquid mixtures of ionic liquids 1-ethyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-butyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [BMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻ or 1-methyl-3-octyl-imidazolium diethyleneglycol monomethylethersulphate [MOIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+methanol and [EMIM]⁺[CH₃(OCH₂CH₂)₂OSO₃]⁻+water at 298.15, 303.15 and 313.15 K. The V _m ^E values were found to be negative for all systems studied. The V _m ^E results are explained in terms of intermolecular interactions and packing effects. The experimental data were fitted by the Redlich-Kister polynomial.     

Synthesis of Unsymmetrical Bissalicylaldimine Ligands and bis-Schiff Base Cobalt Complexes with Benzo-10-aza-15-crown-5 Pendant

Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] salicylaldehyde with the half unit Schiff bases and characterized by ^1H NMR, IR, mass spectroscopy, elemental analysis, molar conductances and molar magnetic susceptibility.     

Synthesis and spectroscopic study of praseodymium(III) complexes with tetra-15-crown-5-phthalocyanine

Praseodymium(III) complexes with tetra-15-crown-5-phthalocyanine—the neutral radical [(R₄Pc^?·)Pr³⁺(R₄Pc^2?)]⁰ and one-electron reduced [(R₄Pc^2?)Pr³⁺(R₄Pc^2?)]^? forms of the sandwich double-decker complex and the triple-decker complex Pr₂(R₄Pc)₃ (R₄Pc^2? is [4,5,4′,5′,4″,5t",4″′,5″′-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion])—have been synthesized and spectrally characterized. These compounds have been obtained by direct interaction of tetra-15-crown-5-phthalocyanine with praseodymium(III) acetate or acetylacetonate. The salt anion has an effect on the yield and structure of the reaction products. The complexes have been obtained in high yields, isolated, and characterized by different physicochemical methods: UV and visible electronic absorption spectroscopy, ¹H NMR, and MALDI-TOF mass spectrometry. The double-decker complex is stable in the solid state and in solutions. The triple-decker complex is stable only in the solid state. In a chloroform-methanol (10 vol %) solution, it slowly decomposes.     

Complexes of benzo-15-crown-5 with protonated primary amines and diamines

Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH₂NH₃(B15C5)](ClO₄), [p-C₆H₄(CH₂NH₃)₂(B15C5)₂](ClO₄)₂, and [(CH₂)₄(NH₃)₂(B15C5)₂](SCN)₂ were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH₃⁺ moiety with characteristic small separation of 1.84-1.86 Å between the nitrogen of the R-NH₃⁺ group and the O₅ mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH₃⁺/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K₁=550±10 M⁻¹ for [PhCH₂NH₃]⁺; K₁=1100±100 and K₂=400±30 M⁻¹ for [p-C₆H₄(CH₂NH₃)₂]²⁺; and K₁=1100±100 and K₂=300±30 M⁻¹ for [H₃N(CH₂)₄NH₃]²⁺. The complexation is primarily enthalpy-driven (ΔH°=−4.9±0.5 kcal/mol, ΔS°=−3.8±1.0 eu for PhCH₂NH₃⁺-B15C5), as determined by variable temperature ¹H NMR titrations.     

Proton-induced supramolecular dimerization of aminomethylbenzo-15-crown-5 accompanied by a covalent dimerization of cyanoborohydride anion

Reductive amination of 4′-formyl[benzo-15-crown-5] with sodium cyanoborohydride in the NH₄Ac/MeOH medium followed by acid addition and extraction with CHCl₃ unexpectedly lead to the isolation of the salt (B15C5-CH₂-NH₃)⁺-(H₃BCNBH₂CN)⁻ with an unusual dicyanodiborohydride anion. The self-complementary 4′-ammoniomethyl[benzo-15-crown-5] cation was found to exist as a supramolecular dimer in the solid state, acetonitrile solution, and gas phase as revealed by X-ray crystallography, NMR and mass spectrometry, respectively.     

Erbium complexes with tetra-15-crown-5-phthalocyanine: Synthesis and spectroscopic study

Erbium mono-, bis-, and tris(phthalocyaninates) with tetra-15-crown-5-phthalocyanine (H₂R₄Pc) were synthesized and studied by spectroscopic methods. The complexes were obtained by reacting H₂R₄Pc with erbium salts in high-boiling solvents. To compare the efficiency of two approaches to the synthesis of double-decker lanthanide phthalocyaninates, bis(phthalocyaninate) [Er(R₄Pc)₂] was also obtained by a template procedure from dicyanobenzo-15-crown-5. A combination of physicochemical methods (UV and IR spectroscopy, MALDI-TOF mass spectrometry, ¹H NMR) was used for identifying the compounds and proving their individuality and structure. The photoluminescence method demonstrated that solutions of erbium bis- and tris(phthalocyaninates) in CHCl₃ are nonfluorescent in the visible range of light whereas solutions of mono(phthalocyaninate) in CHCl₃ and DMSO exhibit fluorescence with maxima at 707 and 695 nm, respectively. The oxidation of erbium mono(phthalocyaninate) leads to fluorescence quenching.     

Synthesis and Characterization of Aminophosphines,Bis(amino)phosphine Derivatives,and Their Molybdenum(0) Complexes

Functionalized bis(amino)phosphines of the type PhP(NHR)₂ ( 1a–c ) and aminophosphines of the type Ph₂PNHR ( 2a–c ) have been synthesized by treating PhPCl₂ or Ph₂PCl with corresponding primary amines of H₂N-R where R = -CH₂SO₃H, -C₆H₄SO₃H, and benzo-15-crown-5. The molybdenum(0) complex of the aminophosphine ( 3 ) has been obtained by reacting cis-[Mo(CO)₄(bipy)] with aminophosphine ( 2c ). The synthesized aminophosphines, bis(amino)phosphines, and the molybdenum(0) complex have been characterized by IR, ¹H NMR, ³¹P NMR, and MS spectroscopic techniques and by elemental analysis.     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4'-磺酰肼苯并-15-冠-5 (2). 后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h, 产物经元素分析, IR, ¹H NMR, ¹³C NMR, MS确证了其结构. 利用紫外－可见吸收光谱考查了其对不同阴离子的识别作用, 结果表明, 化合物3d, 3e, 3h对碱性较强的阴离子有较强的选择性识别作用.     

[Na(15-Krone-5)][ReFCl3(NO)(CH3CN)] Synthese,IR-Spektrum und Kristallstruktur

[Na(15-crown-5)][ReFCl₃(NO)(CH₃CN)] Synthesis, IR Spectrum, and Crystal Structure The title compound has been prepared by the reaction of [ReCl₃(NO)₂(CH₃CN)] with the equivalent amount of sodium fluoride in the presence of 15-crown-5 in boiling acetonitrile, forming blue crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group P2₁/n, Z = 4,2117 observed independent reflections, R = 0.037, wR = 0.029. Lattice dimensions at 20°C: a = 834.0(2), b = 1600.0(3), c = 1670.0(3) pm; β = 104.19(3)°. The compound forms an ion pair via one Na F contact of 234.4 pm and one Na Cl contact of 293.4 pm; the nitrosyl ligand ist in trans-position to the F atom of the anion [ReFCl₃(NO)(CH₃CN)]⁻.     

Synthesis and properties of gemini-type hydrocarbon-fluorocarbon hybrid surfactants

Gemini-type hybrid surfactants with two fluorocarbon chains connected through a hydrocarbon spacer, F(CF₂)_m(CH₂)₂CH(OSO₃Na)(CH₂)_nCH(OSO₃Na)(CH₂)₂(CF₂)_mF [Fm(Hn)FmOS, m = 4, 6; n = 5, 6, 7, 8)], were synthesized and their surface chemical properties were examined with the aim to have highly functional and highly water-soluble fluorinated surfactants when compared with the conventional fluorinated surfactants. Comparisons of the surface chemical properties of the synthesized gemini-type hybrid surfactants with those of monounit-type hybrid surfactants, F(CF₂)_m(CH₂)₂CH(OSO₃Na)(CH₂)_nH [FmEHnOS, m = 4, 6; n = 3, 5)], revealed that gemination causes a remarkable lowering (about 1/100) in cmc value while it produces little changes in Krafft point (below 0 °C) and surface tension at cmc (γ_cmc).     

(Mesitylene)ruthenium π-complexes with benzo-15-crown-5 and dibenzo-18-crown-6

The reactions of benzo-15-crown-5 and dibenzo-18-crown-6 with 1 equiv. of [(mes)Ru(MeNO₂)₃]²⁺ (mes = 1,3,5-C₆H₃Me₃) give the mononuclear complexes [(mes)Ru(η⁶-benzo-15-crown-5)]²⁺ (1) and [(mes)Ru(η⁶-dibenzo-18-crown-6)]²⁺ (2) in 50% yield. Similar reaction with 2 equiv. of [(mes)Ru(MeNO₂)₃]²⁺ produces the dinuclear complex [(μ-η⁶:η⁶-dibenzo-18-crown-6)Ru₂(mes)₂]⁴⁺ (3) in 96% yield as a 2:3 mixture of cis- and trans-isomers. Structures of 2(OTf)₂ and trans-3(OTf)₄ were confirmed by X-ray diffraction. The NMR titration showed that mononuclear dications 1 and 2 bind Na⁺ ion less effective (K_a = 600 and 250 M^-1) than free benzo-15-crown-5 and dibenzo-18-crown-6 (K_a = 2 × 10⁵ and 5 × 10⁶ M⁻¹). The dinuclear tetracation 3 does not bind Na⁺ within measurable limits of NMR titration method. The electrochemical behaviour of complexes 1-3 was studied in propylene carbonate solution. They exhibit a partially chemically reversible Ru(II)/Ru(I) reduction, which in the case of the dinuclear complex 3 proceeds through two slightly separated steps. The redox activity of the complexes is substantially unaffected by the presence of sodium ion.     

Behavior of octa(benzo-15-crown-5)- and tetrasulfophthalocyanines in the presence of water-soluble C60 compounds

Octa[(4′-benzo-15-crown-5)oxy]phthalocyanine was shown to dissolve in the presence of water-soluble fullerene compounds C₆₀Cl(NHCH₂CH₂NH₃ ⁺)₅(^?OOCCF₃)₅ or C₆₀Cl(C₆H₄CH₂CH₂COONa)₅. The solubilization of phthalocyanine was attributed to the possibility of formation of the hydrogen bonds N-H...O(CH₂) and coordination of the sodium cations inside the cavities of the crown ether fragments for the cationic and anionic fullerene derivatives, respectively. Solubilization of the crown-containing phthalocyanine with participation of water-soluble fullerene compounds proceeded with the formation of aggregated forms. A monomeric form of nickel tetrasulfonated phthalocyaninate in the presence of an equimolar amount of C₆₀Cl(NHCH₂CH₂NH₃ ⁺)₅(^?OOCCF₃)₅ in 50% ethanol is transformed into a dimeric form. The structures of the fullerene-containing compounds and their state in solution facilitate the stacking aggregation of phthalocyanines.     

Metathesis of silicon-containing olefins: IX. Synthesis of 1-(trimethylsilyl)-1-alkenes by olefin metathesis

1-(Trimethylsilyl)-1-alkenes of general formula CH₃(CH₂)_nCH?CHSi(CH₃)₃, where n = 3–15, have been prepared by a novel method, viz. by an effective cross-metathesis of vinyltrimethylsilane with 1-alkenes catalyzed by RuCl₂(PPh₃)₃. Excess of 1-alkene in the reaction mixture gave 1-(trimethylsilyl)-1-alkenes in good yields of up to 60% (in terms of vinylsilane). The products were identified by NMR spectroscopic (¹H, ¹³C NMR) and GC MS methods.     

The Homoleptic U(NCSe)84– Anion in (Pr4N)4U(NCSe)8·2CFCl3 and Th(NCSe)4(OP(NMe2)3)4·0.5CH3CN·0.5H2O: First Structurally Characterised Actinide Isoselenocyanates

The neutral thorium complex Th(NCSe)₄(OP(NMe₂)₃)₄ and homoleptic octa(isoselenocyanato)uranate anion U(NCSe)₈^4– in (Pr₄N)₄U(NCSe)₈·2CFCl₃ ( 1 ) were synthesised and structurally characterised. (Pr₄N)₄U(NCSe)₈·2CFCl₃ contains the U^IV anion U(NCSe)₈^4– and was characterised using IR spectroscopy and single‐crystal X‐ray diffraction. Th(NCSe)₄(OP(N(CH₃)₂)₃)₄·0.5CH₃CN·0.5H₂O ( 2 ) was characterised using IR and Raman spectroscopy, as well as ³¹P{¹H}, ¹⁵N{¹H}, ¹⁴N{¹H}, ¹³C{¹H}, ¹H and ⁷⁷Se NMR spectroscopy and structurally characterised using single‐crystal X‐ray diffraction. The U(NCSe)₈^4– anion and Th(NCSe)₄(OP(N(CH₃)₂)₃)₄·0.5CH₃CN·0.5H₂O complex are the first structurally characterised actinide‐isoselenocyanates. The crystal structures shows an approximate square antiprismatic arrangement of the ligands around the actinide(IV) atoms.     

Extraction of barium picrate into nitrobenzene in the presence of benzo-15-crown-5

From extraction experiments with ¹³³Ba as a tracer, the extraction constant corresponding to the equilibrium Ba²⁺(aq) + 2A^-(aq) + 2L(nb) BaL₂ ²⁺(nb) + 2A^-(nb) in the two-phase water-nitrobenzene system (A^- = picrate, L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (BaL₂ ²⁺, 2A^-) = 5.7. Furthermore, the stability constant of the benzo-15-crown-5 - barium complex in nitrobenzene saturated with water was calculated: log b_nb (BaL₂ ²⁺) = 14.6.     

Metal-containing ditopic receptors for molecular recognition of diammonium cations

Two new ditopic receptors for α,ω-alkanediyldiammonium cations based on a tetraazamacrocyclic (cyclidene) nickel(II) complex bearing two crown-ether residues were synthesized. The studies of the host-guest interaction between the receptors and a series of α,ω-diammonium salts by NMR titration in acetonitrile-d₃ showed that 1:1 complexes are formed with K_assoc∼10³-10⁵ M⁻¹. Receptor 1 with benzo-15-crown-5 arms showed substantial selectivity in binding of trimethylene- and tetramethylenediammonium dications, and 1-2 orders of magnitude weaker binding of shorter (C₂) or longer (C₅ and C₆) diammonium cations. Receptor 2 with benzo-18-crown-6 arms showed higher affinity to all studied diammonium cations, but the recognition of the length of α,ω-diammonium cations was less pronounced.