Synthesis of 6-mono-6-deoxy-beta-cyclodextrins substituted with isomeric aminobenzoic acids. Structural characterization, conformational preferences, and self-inclusion as studied by NMR spectroscopy in aqueous solution and by X-ray crystallography in the solid state

The synthesis, purification, and characterization of mono-6-modified-beta-cyclodextrins bearing N-attached o-, m-, and p-aminobenzoic acids (2, 3, and 4, respectively) are presented. The structures in aqueous solution were investigated using one- and two-dimensional NMR spectroscopy. Detailed assignment of the spectra together with intramolecular NOE correlations revealed the way each of the isomeric appendages is positioned relative to the macrocyclic cavity. No self-inclusion is observed. The o-isomer 2 turns inward over the top of the primary side and interacts with specific protons of the substituted glucopyranose unit A and those of a neighboring unit. The m-isomer 3 displays two conformations, where the substituent resides above the primary side in a tilted manner and interacts either with the previous or the next unit. We propose that the carboxyl groups in both 2 and 3 are localized through H-bonding with one or two, respectively, primary hydroxyl groups of the neighboring glucopyranose units. In a similar positioning of the aromatic ring of the p-isomer 4, the hydrophilic carboxyl end is fully exposed to the aqueous environment. The X-ray structure of 4 shows that the solution conformation has evolved such that in the crystalline state, the aromatic moiety is inserted through its carboxyl part inside another CD where it establishes intermolecular H-bonds with inward-turned primary OH groups. Besides this stabilization, 4 forms parallel and antiparallel supramolecular chains in the crystal that are additionally stabilized by direct H-bonds.     

Synthesis and characterization of two cyclic organosiloxanes by multinuclear NMR spectroscopy and X-ray crystallography

1,3-[2′,6′-Pyridinebis(methyleneoxy)]-1,3-bis(diphenyl)cyclodisiloxane (9) and 2,6-pyridinebis(1,1-diphenylethoxy)diphenylsilane (11) were obtained from 2,6-pyridinediol derivatives with dichlorodiphenylsilane. An N→Si interaction is present in 2,6-pyridinebis(1,1-diphenylethoxy)diphenylsilane, which also shows fluxional behavior. The activation energy of 13.2 kcal mol⁻¹ for 11 was obtained for the intramolecular exchange between the phenyl groups from a variable-temperature ¹H-NMR study. The compounds were characterized by ¹H-, ¹³C- and ²⁹Si-NMR and their structures were established by X-ray crystallographic studies.     

Combinatorial multinuclear NMR and X-ray diffraction studies of uranium(VI)-nucleotide complexes

The complex formation of uranium(VI) with four nucleotides, adenosine- (AMP), guanosine- (GMP), uridine- (UMP), and cytidine-monophosphate (CMP), has been studied in the alkaline pH range (8.5-12) by (1)H, (31)P, (13)C, and (17)O NMR spectroscopy, providing spectral integral, chemical shift, homo- and heteronuclear coupling, and diffusion coefficient data. We find that two and only two complexes are formed with all ligands in the investigated pH region independently of the total uranium(VI) and ligand concentrations. Although the coordination of the 5'-phosphate group and the 2'- and 3'-hydroxyl groups of the sugar unit to the uranyl ions is similar to that proposed earlier ("Feldman complex"), the number and the structures of the complexes are different. The uranium-to-nucleotide ratio is 6:4 in one of the complexes and 3:3 in the other one, as unambiguously determined by a combinatorial approach using a systematic variation of the ratio of two ligands in ternary uranium(VI)-nucleotide systems. The structure of the 3:3 complex has been determined by single-crystal diffraction as well, and the results confirm the structure proposed by NMR in aqueous solution. The results have important implications on the synthesis of oligonucleotides.     

Ruthenium agostic (phosphinoaryl)borane complexes: multinuclear solid-state and solution NMR, X-ray, and DFT studies

The reactivity of the (o-phosphinophenyl)(amino)borane compound HB(N(i)Pr(2))C(6)H(4)(o-PPh(2)) prepared from Li(C(6)H(4))PPh(2) and HBCl(N(i)Pr(2)) toward the bis(dihydrogen) complex RuH(2)(H(2))(2)(PCy(3))(2) (1) was studied by a combination of DFT, X-ray, and multinuclear NMR techniques including solid-state NMR, a technique rarely employed in organometallic chemistry. The study showed that the complex RuH(2){HB(N(i)Pr(2))C(6)H(4)(o-PPh(2))}(PCy(3))(2) (3), isolated in excellent yield as yellow crystals and characterized by X-ray diffraction, led in solution to PCy(3) dissociation and formation of an unsaturated 16-electron complex RuH(2){HB(N(i)Pr(2))C(6)H(4)(o-PPh(2))}(PCy(3)) (4), with a hydride trans to a vacant site. In both cases, the (phosphinoaryl)(amino)borane acts as a bifunctional ligand through the phosphine moiety and a Ru-H-B interaction, thus featuring an agostic interaction.     

The structure of 1-formyl-3-phenyl-Δ-pyrazoline in the gas phase (DFT calculations), in solution (NMR) and in the solid state (X-ray crystallography)

The molecular structure of 1-formyl-3-phenyl-Δ²-pyrazoline was determined by X-ray crystallography (triclinic, P-1). The geometry thus obtained was compared with that obtained by DFT calculations. The GIAO method was used to calculate absolute shieldings, which agree conveniently with those measured by ¹³C and ¹⁵N NMR. The title compound appears to be an essentially planar molecule.     

Helix change of polypeptides in the solid state as studied by NMR spectroscopy

The conformational characterization of solid polypeptides has been carried out by means of high-resolution solid-state NMR. It has been demonstrated that high-resolution solid-state NMR spectroscopy is a very useful means for elucidating the structure of polypeptides and proteins in the solid state.     

Multicomponent polyanions. 45. A multinuclear NMR study of vanadate(V)-oxalate complexes in aqueous solution.

The two complexes formed in the aqueous vanadooxalate system, V(Ox)- and V(Ox)2(3-), have been characterized using 51V, 13C and 17O NMR. For the V(Ox)2(3-) complex, two peaks are observed in 13C NMR and four in 17O NMR. This leads to the conclusion that each oxalate ligand has two different distances to the VO2 group. This fact, together with the peak integrals and the chemical shifts, indicates strongly that the hexacoordinate complex [VO2(C2O4)2]3- found in single-crystal X-ray structure determinations persists in aqueous solution. The dependence of the 13C NMR linewidths upon temperature reveals two types of dynamic processes: (1) a rearrangement in which the two different V-Oox switch places and (2) an exchange of the oxalate ligands in the [VO2(C2O4)2]3- complex with free oxalate, probably through a dissociative process. Rate constants and activation parameters for the two dynamic processes involving [VO2(C2O4)2]3- have been calculated from the shape of the 13C NMR signals. For the V(Ox)- complex, only one relatively narrow peak is obtained in 13C NMR and three peaks in 17O. This fact, as well as the relative positions of these peaks, is in accordance with a pentacoordinate complex [VO2(C2O4)H2O]-, where the two V-O distances to the oxalate ligand are equal. We also show that, in the pH range 0.8-6.6, there is no protonation of the studied complexes, in agreement with previous potentiometric results.     

Water exchange in fluoroaluminate complexes in aqueous solution: a variable temperature multinuclear NMR study

An 17O, 19F, and 27Al NMR study of fluoroaluminate complexes (AlFn(H2O)6-n((3-n)+), n = 0, 1, and 2) in aqueous solution supports the idea that for each substitution of a bound water molecule by a fluoride anion, the exchange rate of bound water with free water increases by about 2 orders of magnitude. New rate coefficients for exchange of inner-sphere water molecules in AlF(H2O)5(2+) are kex(298) = 230(+/-20) s(-1), DeltaH(dagger) = 65(+/-3) kJ mol(-1), and DeltaS(dagger) = 19(+/-10) J mol(-1) K(-1). The corresponding new values for the AlF2(H2O)4(+) complex are: kex(298) = 17 100(+/-500) s(-1), DeltaH(dagger) = 66(+/-2) kJ mol(-1), and DeltaS(dagger) = 57(+/-8) J mol(-1) K(-1). When these new results are combined with those of our previous study,(4) we find no dependence of the solvent exchange rate, in either AlF(H2O)5(2+) or AlF2(H2O)4(+), on the concentration of fluoride or protons over the range of SigmaF = 0.06-0.50 M and [H(+)] = 0.01-0.44 M. A paramagnetic shift of 27Al resonances results from addition of Mn(II) to the aqueous solution as a relaxation agent for bulk waters. This shift allows resolution of the AlFn(H2O)6-n((3-n)+) species in 27Al NMR spectra and comparison of the speciation determined via thermodynamic calculations with that determined by 27Al, 19F, and 17O NMR.     

The hydration of the scandium(III) ion in aqueous solution and crystalline hydrates studied by XAFS spectroscopy, large-angle X-ray scattering and crystallography

The structures of the hydrated scandium(III) ion and of the hydrated dimeric hydrolysis complex, [Sc2(mu-OH)2]4+, in acidic aqueous solutions have been characterized by X-ray absorption fine structure (XAFS) and large-angle X-ray scattering (LAXS) methods. Comparisons with crystalline reference compounds containing hydrated scandium(III) ions in well characterized six-, seven- and eight-coordinated polyhedra have been used to evaluate the coordination numbers and configurations in aqueous solution. In strongly acidic aqueous solution the structure of the hydrated scandium(III) ion is found to be similar to that of the eight-coordinated scandium(III) ion with distorted bicapped trigonal prismatic coordinating geometry in the crystalline [Sc(H2O)(8.0)](CF3SO3)3 compound. The EXAFS data reveal for the solution, as for the solid, a mean Sc-O bond distance of 2.17(1) Angstrom to six strongly bound prism water molecules, 2.32(4) Angstrom to one capping position, with possibly another capping position at about 2.5 Angstrom. The LAXS study supports this structural model and shows furthermore a second hydration sphere with approximately 12 water molecules at a mean Sc...O(II) distance of 4.27(3) Angstrom. In less acidic concentrated scandium(III) aqueous solutions, the dimeric hydrolysis product, [Sc2(mu-OH)2(H2O)10]4+, is the predominating species with seven-coordinated scandium(III) ions in a double hydroxo bridge and five terminal water molecules at a mean Sc-O bond distance of 2.145 Angstrom. Hexahydrated scandium(III) ions are found in the crystal structure of the double salt [Sc(H2O)6][Sc(CH3SO3)6], which crystallizes in the trigonal space group R3[combining macron] with Z = 6 and the unit cell dimensions a = 14.019(2) and c = 25.3805(5) Angstrom. The Sc-O distances in the two crystallographically unique, but nearly identical, [Sc(H2O)6]3+ entities (both with 3[combining macron] imposed crystallographic symmetry) are 2.085(6) and 2.086(5) Angstrom, while the mean Sc-O distance in the near octahedral [Sc(OSO2CH3)6]3- entities (with three-fold symmetry) is 2.078 Angstrom.     

A multinuclear NMR study in the solid state and in solution of thallium(I) tris-(pyrazol-1-yl)borates (thallium scorpionates)

The ¹H, ¹³C and ¹⁵N NMR spectroscopic properties of six thallium tris-(pyrazol-1-yl)borates, including a tetrakis derivative, were determined. The results in solution were necessary to understand those, more complicated, in the solid state. A collection of ²⁰⁵Tl-¹⁵N and ²⁰⁵Tl-¹³C couplings was measured in the latter state. Among those, a very large coupling constant (between 194 and 282 Hz) has been measured on the carbon at the position 4 of the pyrazole ring in several compounds and particularly for the cyclobutyl derivative [Tl(Tp^Cbu)]. It has been assigned to a direct interaction of the 4-C-H ? Tl type and related to the X-ray structures, when available.     

Solid state complexes of nickel(II) and 4-imidazoleacetic acid: X-ray crystallography and spectroscopic investigation

The stoichiometric reaction of NiCl₂·6H₂O with sodium 4-imidazoleacetate Na(IA) in absolute MeOH yields blue crystals of Ni(IA)₂·4H₂O·2MeOH (1). This product decomposes rapidly in air, losing two MeOH molecules and producing Ni(IA)₂·4H₂O (2). Compound (1) when left in the mother liquor, slowly recrystallizes forming [Ni(IA)₂(MeOH)₂] (3), which is stable in air and suitable for single crystal X-ray diffraction studies. These crystals consist of slightly distorted octahedral coordination units in which the carboxylic oxygen, imidazole N3 nitrogen and the MeOH oxygen atoms act as coordination centers. The i.r. features, due to MeOH molecules, were employed to characterize the compounds studied. The reflectance spectrum of (3) was interpreted on the basis of octahedral and tetragonal symmetry of the NiO₄N₂ chromophore.     

Np(V) carbonates in solid state and aqueous solution

The solubility of NaNpO₂CO₃(s) in 0.1M perchlorate solution at 25°C in equilibrium with 1.0% CO₂/N₂ atmosphere has been investigated as a function of pH/lg [CO₃ ^2-]. The solid phase was found hexagonal with a=1008.1±0.3 pm and c=991.1±0.2 pm. A solubility product of lg Ksp(NaNpO₂CO₃)=–10.22±0.02 and a formation constant of the first Np(V) carbonato species of lg ß₀₁ = 4.52±0.02 was evaluated. For the dicarbonato species an upper limit of lg lg ß₀₂ < 6.6 was derived. Comparison of the present data with solubility values of Np(V) in equilibrium with 0.03% CO₂ partial pressure gave evidence that carbonato species are prevailing in solutions at both 1% and 0.03% CO₂ partial pressures.     

Potentiometric and multinuclear NMR studies on the interaction of aluminum with ascorbic acid in acidic aqueous solution

The complex-formation equilibria between aluminum(III) ion and L-(+)-ascorbic acid (AA) in 0.1 M KCl ionic medium at 25 degrees C and 0.15 M NaCl ionic medium at 37 degrees C were studied by glass electrode pH-metric measurements. The obtained experimental results were explained by the formation of the following complexation species: a weak mononuclear 1:1 species AlL(2+) together with two trinuclear mixed-hydroxo species Al(3)H(-5)L(4) and Al(3)H(-5)L(3+) in acidic aqueous solutions. Meanwhile, the formation of the complexes and structures of Al with AA were proved by multinuclear (1H, 13C, 27Al) NMR spectra in the pH range 2.0-5.0. It is supposed that Al directly coordinates with AA at O-3 moiety; also, Al can coordinate with the O-1 and O-2 moieties of ascorbate ion through the weakly binding and the intramolecular hydrogen bonding in acidic aqueous solutions.     

Thermodynamic and multinuclear magnetic resonance study of dimethyltin (IV) complexes with some imidazoles in aqueous solutions

The interaction between imidazole (L1), 2-isopropylimidazole (L2), 2-amino-benzimidazole (L3) and 2-(2-pyridyl)benzimidazole (L4) (L in general), and dimethyltin chloride in water have been investigated at 25 degrees C and ionic strength of 0.1 M sodium nitrate using the potentiometric technique. The results showed the formation of 1:1 and 1:2 (organotin:ligand) complexes and the corresponding stability constants were determined. The effect of the pKa values of the respective ligands on the stability constants of its complex species was elucidated. The concentration distribution of the complexes in solution was evaluated. Also, their solid complexes of the general formula in diethylether-dichloromethane, give 1:2 (organotin:Ligand) [(L)2 (CH3)2 SnCl2.zH2O][L = L1, z = 0 and L = L2, z = 1] and 1:1 [L (CH3)2 SnCl2.zH2O][L = L3, z = 0 and L = L4, z = 2]. The separated solid products were characterized by elemental analyses (C, H, N, Cl), IR, mass spectra, thermogravimetric analysis (TGA) and magnetic susceptibility. The participation of the ligand functional groups in bonding to the organotin (IV) was discussed. Conductivity and 1H-NMR spectra were used to confirm the behaviour of these complexes in solution.     

Insights into the acid-base properties of Pt(IV)-diazidodiam(m)inedihyroxido complexes from multinuclear NMR spectroscopy

Platinum(IV) am(m)ine complexes are of interest as potential anticancer pro-drugs, but there are few reports of their acid-base properties. We have studied the acid-base properties of three photoactivatable anticancer platinum(IV)-diazidodiam(m)ine complexes (cis,trans,cis-[Pt(IV)(N(3))(2)(OH)(2)(NH(3))(2)], trans,trans,trans-[Pt(IV)(N(3))(2)(OH)(2)(NH(3))(2)], and cis,trans-[Pt(IV)(N(3))(2)(OH)(2)(en)]) using multinuclear NMR methods and potentiometry. In particular, the combination of both direct and indirect techniques for the detection of (15)N signals has allowed changes of the chemical shifts to be followed over the pH range 1-11; complementary (14)N NMR studies have been also carried out. A distinct pK(a) value of approximately 3.4 was determined for all the investigated complexes, involving protonation/deprotonation reactions of one of the axial hydroxido groups, whereas a second pH-dependent change for the three complexes at approximately pH 7.5 appears not to be associated with a loss of an am(m)ine or hydroxido proton from the complex. Our findings are discussed in comparison with the limited data available in the literature on related complexes.     

Photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in aqueous solution

The photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in an aqueous solution has been studied under irradiation at long wavelengths (at λ ≥ 300 nm) and in the presence of oxygen, as these conditions of irradiation are those of natural outdoor aging. Infrared spectroscopy was used to follow the photochemical evolution of the polymer either for solid films of PVP or for PVP irradiated in an aqueous solution. Chemical treatments (NH₃, SF₄) were carried out on the photooxidized samples, and aqueous solutions of PVP were characterized by viscometry and size exclusion chromatography (SEC). Based on photooxidation results obtained in both the solid state and in an aqueous solution, a general mechanism that accounts for the main routes of oxidation is proposed. It was shown that the rates of oxidation and the stoichiometries of the reactions were strongly influenced by the physical state of the polymer (solid state or aqueous solution).     

Polymorphism of phenylpyruvic acid studied by IR, Raman and solid state C NMR spectroscopy

Polymorphs I and II of phenylpyruvic acid are obtained as mixtures of both crystal forms or relatively pure crystals, from different solvents. Polymorph I is more stable than polymorph II at room temperature. Spectral characteristics of these polymorphs are discussed on the basis of IR, Raman and solid state ¹³C NMR spectra. Also, the assignment of the IR features observed in the 1600–1700 cm⁻¹ region is re-investigated by referring to the spectra of heavy-atom substituted derivatives. It is suggested that the C=O stretching band is split by the crystal field for both polymorphs.     

Epr studies of copper(II) and oxovanadium(IV) dithiophosphate complexes in the solid state

A single crystal of Cu(dtp)₂ and numerous powdered copper(II) and oxovanadium(IV) dithiophosphate complexes magnetically diluted in the corresponding Ni and In complexes have been prepared and studied by EPR. It was shown that the values of A(³¹P) for all complexes are isotropic.Some assumptions about the origin of superhyperfine splitting in the EPR spectra of the complexes are discussed.     

Hexahalogenotin(IV) complexes in aqueous mixed hydrogen halide solutions in the glassy state

The configurations of hexahalogenotin(IV) complex ions in glassy aqueous mixed hydrogen halide solutions were determined by Mössbauer and Raman spectroscopies. Trans-(SnF₄Cl₂)^2-, (SnCl₅Br)^2- and (SnCl₅Br)^2- and trans-(SnF₄Br₂)^2- ions are the main tin complex ions in the aqueous Sn(IV)-HF-HCl, Sn(IV)-HCl-HBr and Sn(IV)-HF-HBr solutions in the glassy state, respectively.