Missing-link macrocycles: hybrid heterocalixarene analogues formed from several different building blocks

The synthesis and structural characterization of hybrid heterocalix[4]arene analogues containing pyrrole, benzene, methoxy-substituted benzene, and pyridine subunits is described. Macrocycles 1 and 2, examples of calix[2]benzene[2]pyrrole and calix[1]benzene[3]pyrrole systems, respectively, are synthesized by the condensation of pyrrole and an appropriate phenylbis(carbinol). Macrocycles 3 and 7, examples of calix[2]benzene[1]pyridine[1]pyrrole and calix[1]pyridine[3]pyrrole, respectively, are synthesized by the use of a carbene-based pyrrole-to-pyridine ring-expansion procedure. Single-crystal X-ray analysis reveals that compounds 1a, 1b, and 2b adopt 1,3-alternate conformations in the solid state, whereas compounds 3 and 7 display structures that are best described as "flattened partial cones" in terms of their conformation. (Series a refers to pure benzene-derived systems, whereas series b indicates macrocycles containing 5-methoxyphenyl subunits). In the solid state, the methoxy-functionalized macrocycles 1b and 2b, and the chloropyridine-containing macrocycle 7 exist as dimers. In the case of 1a and 7, these compounds interact with neutral solvent in the solid state. The conformations of the macrocycles in solution were explored by temperature-dependent proton NMR and NOESY spectral analysis. At 188 K, macrocycles 1a and 2a adopt flattened 1,3-alternate conformations, whereas macrocycles 3 and 7 exist in the form of flattened partial-cone conformations. Standard proton NMR titration analyses were carried out in the case of macrocycles 1a and 2a, and reveal that at least the second of these systems is capable of binding fluoride and chloride anions in CD(2)Cl(2) solution at room temperature (K(a)=571 and 17M(-1) in the case of 2a and F(-) and Cl(-), respectively).     

Factors controlling the drop evaporation constant

In this paper, we discuss the factors affecting drop evaporation. We found that the droplet morphology at a specific temperature was controlled by the physical properties of the liquid itself, such as the molecular weight, density, diffusion coefficient in air, and heat of vaporization. Two processes are included in drop evaporation: diffusion of liquid molecules into the air (diffusion part) and flow of the liquid molecules from inside the drop to the free outer shell liquid layer within the liquid-vapor interface (evaporation part). The diffusion part remained steady during drying and was not sensitive to the variation of temperature. The evaporation part, however, was an active factor and determined the differences in drop evaporation behaviors.     

Aqueous synthesis of derivatized cyclopentadienyl complexes of technetium and rhenium directed toward radiopharmaceutical application

Half-sandwich complexes of the type [(RCOCp)M(CO)(3)] with M = Re and (99(m))Tc were synthesized from [M(OH(2))(3)(CO)(3)](+) in water. The R group can be an organic residue or a receptor binding biomolecule with a spacer to cyclopentadienyl (Cp). This provides a general route to Cp complexes of technetium without the need for starting from [TcBr(CO)(5)]. The X-ray structure of [(C(6)H(5)CH(2)COC(5)H(4))Tc(CO)(3)] has been elucidated. The compound crystallizes in the monoclinic space group P2(1)/c with a = 16.1454(9), b = 7.6300(6), and c = 12.3922(7) A and beta = 107.792(6) degrees. We have chosen a serotonergic receptor ligand (WAY) as an example for the derivatization of Cp with a bioactive molecule. WAY is linked to Cp by an aliphatic chain of variable length. The half-sandwich complexes were prepared from water and organic solvents. The structure of [(WAY4-Cp)Re(CO)(3)] could be elucidated. The compound crystallizes in the monoclinic space group P2(1)/c with a = 15.7112(6), b = 6.8775(3), and c = 25.5217(12) A and beta = 103.778(5) degrees. Quantification of inhibition constants gave a clear structure-activity relationship. A single methylene group between the receptor binding site and the half-sandwich complex gave an IC(50) of 217 nM for HT(1A), whereas a butylene linker resulted in retention of the inhibition constant with an IC(50) of 6 nM with respect to underivatized WAY. For use as radiopharmaceuticals, the compounds have also been prepared with (99m)Tc in quantitative yield.     

Metal complexes of porphycene,corrphycene, and hemiporphycene: stability and coordination chemistry

Porphyrin (P), porphycene (Pc), corrphycene (Cn), and hemiporphycene (Hpc) represent a series of well defined "4-N in" constitutional porphyrin isomers. These isomers, in the form of their octaethyl derivatives, represent a congruent set of porphyrinoids whose properties can be compared. In this study we report how variations in electronic structure and nitrogen-core size in the free-base forms of these four systems are reflected in the properties of their corresponding metal complexes. Specifically, the effects that these differences have on the axial ligation properties of the Zn(II), Mg(II), Ni(II), and Co(II) complexes of P, Pc, Cn, and Hpc in toluene using pyridine as the axial ligand are detailed. Also reported are the relative stabilities of these complexes under acidic conditions. It is shown that for the zinc, magnesium, and cobalt complexes, there are distinct differences in the ability to maintain four-, five-, or six-coordinate geometries in the presence of similar concentrations of pyridine. By contrast, no apparent differences in axial ligand binding affinity are seen for the four nickel complexes. Little difference in stability was likewise seen when these same complexes were subject to acid-mediated demetallation, with all four falling into stability class II, according to the accepted porphyrin stability ranking system. High stabilities were also seen in the case of the cobalt complexes, with the Pc and Cn complexes being of stability class III and the P and Hpc derivatives falling into stability class II. The Zn(II) and Mg(II) complexes were all far less stable than the corresponding Ni(II) and Co(II) complexes. In this case, semiquantitative analyses of the rate of acid-induced decomposition revealed the following stability sequence P>Cn>Hpc>Pc for both the Zn(II) and Mg(II) complexes. Single-crystal X-ray diffraction structures were solved for the Zn(II), Mg(II), and Ni(II) complexes of the octaethyl derivatives of Hpc, Cn, and Pc as well as a Co(II) octamethylcorrphycene and are reported as part of this study. These solid-state structures confirm four-coordinate species for the Ni(II) complexes, four- and five-coordinate species for the Mg(II) and Zn(II) complexes, and a six-coordinate species for the lone Co(II) complex.     

Experimental and computational studies of trialkylaluminum and alkylaluminum chloride reactions with silica

Reactions of trimethylaluminum, triethylaluminum, and diethylaluminum chloride and ethylaluminum dichloride with silica gel have been studied experimentally by infrared spectroscopy and elemental analysis. The silica gel was subjected to different pretreatments to alter surface functionalities prior to reaction. In all cases the extent of surface modification reaction follows the trend unmodified > 600 degrees C pretreated > hexamethyldisilazane (HMDZ) pretreated > 600 degrees C/HMDZ pretreated. All of the aluminum compounds studied completely react non-hydrogen-bonded silanols, while also reacting with hydrogen-bonded silanols and siloxanes. Primarily monomeric surface species result from the surface modification reaction. Ethylaluminum chlorides preferentially react with silanols through cleavage of the Al-C bond rather than the Al-Cl bond. Singly bonded Si(s)-O-AlCl(2) surface species are readily synthesized by reaction of ethylaluminum dichloride with HMDZ-pretreated silica gel. Bridged bonded (Si(s)-O)(2)-AlCl surface species are readily synthesized by reaction of diethylaluminum chloride with HMDZ-pretreated silica gel. Computational ab initio studies of the cluster Si(4)O(6)(OH)(4) as a model to study the reaction of monomeric and dimeric methylaluminum dichloride with a silica silanol are also described. Comparison of the potential energy surface (PES) of monomer and dimer indicates that the energetics favor monomer reaction, consistent with experimental results. The energy cost in the dimer reaction is primarily from cleavage of a bridged Al-Cl bond upon adsorption. This does not occur when the monomer adsorbs. A comparison of the PES for the two reaction pathways resulting from cleavage of either an Al-Cl or Al-C bond indicates that while the former reaction is slightly kinetically favored (E(a) = 23.1 kJ/mol for Al-Cl bond cleavage versus E(a) = 31.1 kJ/mol for Al-C bond cleavage), the latter is strongly thermodynamically favored with an overall free energy difference between the two reaction pathways of 135 kJ/mol favorable to Al-C bond cleavage. These reactions are thermodynamically controlled.     

Molten salt flux synthesis and structure of the new layered uranyl tellurite, K4[(UO2)5(TeO3)2O5]

The reaction of UO₃ and TeO₃ with a KCl flux at 800 °C for 3 days yields single crystals of K₄[(UO₂)₅(TeO₃)₂O₅]. The structure of the title compound consists of layered, two-dimensional sheets arranged in a stair-like topology separated by potassium cations. Contained within these sheets are one-dimensional uranium oxide ribbons consisting of UO₇ pentagonal bipyramids and UO₆ tetragonal bipyramids. The ribbons are in turn linked by corner-sharing with trigonal pyramidal TeO₃ units to form sheets. The lone-pair of electrons from the TeO₃ groups are oriented in opposite directions with respect to one another on each side of the sheets rendering each individual sheet nonpolar. The potassium cations form contacts with nearby tellurite units and axial uranyl oxygen atoms. Crystallographic data (193 K, MoKα, ): triclinic, space group , , , , α=99.642(1)°, β=93.591(1)°, γ=100.506(1)°, , Z=1,R(F)=4.19% for 149 parameters and 2583 reflections with I>2σ(I).     

Platinum(IV)-mediated nitrile-sulfimide coupling: a route to heterodiazadienes

Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.     

Ab initio rotation-vibration spectra of HCN and HNC

We have calculated an ab initio HCN/HNC linelist for all transitions up to J= 25 and 18000 cm(-1) above the zero point energy. This linelist contains more than 200 million lines each with frequencies and transition dipoles. The linelist has been calculated using our semi-global HCN/HNC VQZANO + PES and dipole moment surface, which were reported in van Mourik et al. (J. Chem. Phys. 115 (2001) 3706). With this linelist we synthesise absorption spectra of HCN and HNC at 298 K and we present the band centre and band transition dipoles for the bands which are major features in these spectra. Several of the HCN bands and many of the HNC bands have not been previously studied. Our line intensities reproduce via fully ab initio methods the unusual intensity structure of the HCN CN stretch fundamental (00(0)1) for the first time and also the forbidden (02(2)0) HCN bending overtone. We also compare the J = 1-->0 pure rotational transition dipole in the HCN/HNC ground and vibrationally excited states with experimental and existing ab initio results.     

Protonation of Chloro-, Bromo- and Iodo-pentacyanocobaltate(III) Complexes

The reactions between Fe(Phen)₃²⁺[phen = tris-(1,10) phenanthroline] and Co(CN)₅X³⁻ (X = Cl, Br or I) have been studied in aqueous acidic solutions at 25 °C and ionic strength in the range I = 0.001–0.02 mol dm⁻³ (NaCl/HCl). Plots of k₂ versus √I, applying Debye–Huckel Theory, gave the values −1.79 ± 0.18, −1.65 ± 0.18 and 1.81 ± 0.10 as the product of charges (Z_AZ_B) for the reactions of Fe(Phen)₃²⁺ with the chloro-, bromo- and iodo- complexes respectively. Z_AZ_B of ≈ −2 suggests that the charge on these Co^III complexes cannot be −3 but is −1. This suggests the possibility of protonation of these Co^III complexes. Protonation was investigated over the range [H⁺] = 0.0001 −0.06 mol dm⁻³ and the protonation constants K_a obtained are 1.22 × 10³, 7.31 × 10³ and 9.90 × 10² dm⁶ mol⁻³ for X = Cl, Br and I, respectively.     

Liquid chromatographic analysis of vitamin B6 in reconstituted infant formula: collaborative study

A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials.