The synthesis of diene and of vinyl copolymers containing predetermined quantities of polynuclear hydrocarbon or heterocyclic adducts—I. The formation and stability toward tetrahydrofuran of alkali metal salts of polynuclear hydrocarbons

The formation and stabilities of complexes formed in THF between various polynuclear hydrocarbons and excess sodium and lithium metal have been studied. Anthracene and acenaphthylene, which possess high electron affinities, form dianions with either metal whilst phenanthrene forms the dianion only with lithium. Both phenanthrene and naphthalene give solely radical ions on reaction with sodium; it is found that the formation of the naphthalene dianion with lithium is inversely dependent on the naphthalene concentration.The radical anions of all four polynuclear hydrocarbons are relatively stable to the THF solvent whereas the dianions react appreciably in a matter of days to form a variety of adducts and derivatives which have been isolated and identified by NMR spectroscopy.     

Gas-phase stability of derivatives of the closo-hexaborate dianion B(6)H(6)(2-)

B(6)H(6)(2-) does not represent a stable gas-phase dianion, but emits spontaneously one of its excess electrons in the gas phase. In this work we address the question whether small stable gas-phase dianions can be constructed from the parent B(6)H(6)(2-) dianion by substitution of the hydrogens with appropriate ligands. Various hexa-, tetra-, and disubstituted derivatives B(6)L(6)(2-), B(6)H(2)L(4)(2-), and B(6)H(4)L(2)(2-) (L = F, Cl, CN, NC, or BO) are investigated with ab initio methods in detail. Four stable hexasubstituted B(6)L(6)(2-) (L = Cl, CN, NC, or BO) and three stable B(6)H(2)L(4)(2-) (L = CN, NC, or BO) gas-phase dianions could be identified and predicted to be observable in the gas phase. The trends in the electron-detachment energies depending on various ligands are discussed and understood in the underlying electrostatic pattern and the electronegativities of the involved elements.     

Stable aromatic dianion in water

Perylene diimide (PDI) bearing polyethylene glycol substituents at the imide positions was reduced in water with sodium dithionite to produce an aromatic dianion. The latter is stable for months in deoxygenated aqueous solutions, in contrast to all known aromatic dianions which readily react with water. Such stability is due to extensive electron delocalization and the aromatic character of the dianion, as evidenced by spectroscopic and theoretical studies. The dianion reacts with oxygen to restore the parent neutral compound, which can be reduced again in an inert atmosphere with sodium dithionite to give the dianion. Such reversible charging renders PDIs useful for controlled electron storage and release in aqueous media. Simple preparation of the dianion, reversible charging, high photoredox power, and stability in water can lead to development of new photofunctional and electron transfer systems in the aqueous phase.     

Diastereomer assignment of an olefin-linked bis-paracyclophane by ion mobility mass spectrometry

trans-1,2-Bis([2.2]paracyclophanyl)ethene (1) exists as a pair of diastereomers whose conformations, and thus effective collision cross sections, are quite different. The two forms can be obtained by different transition metal-catalyzed reactions. To assign meso and racemic structures, a novel method is reported in which experimental gas-phase ion mobility data are compared with theoretical structures obtained from molecular mechanics calculations.     

Gas-phase acidities and O-H bond dissociation enthalpies of phenol, 3-methylphenol, 2,4,6-trimethylphenol, and ethanoic acid

Energy-resolved, competitive threshold collision-induced dissociation (TCID) methods are used to measure the gas-phase acidities of phenol, 3-methylphenol, 2,4,6-trimethylphenol, and ethanoic acid relative to hydrogen cyanide, hydrogen sulfide, and the hydroperoxyl radical using guided ion beam tandem mass spectrometry. The gas-phase acidities of Delta(acid)H298(C6H5OH) = 1456 +/- 4 kJ/mol, Delta(acid)H298(3-CH3C6H4OH) = 1457 +/- 5 kJ/mol, Delta(acid)H298(2,4,6-(CH3)3C6H2OH) = 1456 +/- 4 kJ/mol, and Delta(acid)H298(CH3COOH) = 1457 +/- 6 kJ/mol are determined. The O-H bond dissociation enthalpy of D298(C6H5O-H) = 361 +/- 4 kJ/mol is derived using the previously published experimental electron affinity for C6H5O, and thermochemical values for the other species are reported. A comparison of the new TCID values with both experimental and theoretical values from the literature is presented.     

Collisional electron transfer to photoexcited acceptor radical anions

In this article, we show that photoexcitation of radical anions facilitates electron transfer from sodium atoms in femtosecond encounters. Thus, excitation of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and fluorinated TCNQ (TCNQ-F(4)) anions to the second optically active state at 478 nm led to increases in the yields of dianions of about 20% and 10%, respectively. Photoexcitation with a nanosecond-long laser pulse was done a few microseconds before the ions entered the sodium collision cell so that none of the ions would be in any of the initially reached doublet-excited states. We suggest an explanation for the higher electron capture cross section based on the formation of long-lived quartet state anions. Excitation of TCNQ anions within the lowest-energy absorption band, where there are no accessible quartet states, led instead to a lower yield of dianions. There are at least three explanations for the lower dianion yields: (1) Depletion of the monoanion beam due to photodetachment after the absorption of minimum two photons; (2) Formation of short-lived vibrationally excited dianions that decay by electron autodetachment prior to identification; and (3) Lower electron capture cross sections of vibrationally excited monoanions. Similar losses in dianion signal can occur at 478 nm so the actual yield of dianions at this wavelength due to the population of quartet states is therefore greater than that observed. Our methodology devises a more efficient route for the production of molecular dianions, and at the same time it may provide information on long-lived electronic states.     

Coulomb explosion upon electron attachment to a four-coordinate monoanionic metal complex

Electron capture to monoanionic metal complexes in high-energy collisions with sodium vapor is shown to occur with the formation of dianions. In this way, we prepared the small dianions Cr(SCN)42-, Fe(CN)42-, Pt(NO2)22-, and Pt(C2O4)22- in the gas phase. The Cr(SCN)42- dianion Coulomb explodes into Cr(SCN)3- and SCN- with a release of kinetic energy (3.2 +/- 0.4 eV) into translational energy of the fragments. The scheme provides a way to study charge dissociation reactions of molecular dianions that are too short-lived to survive extraction from the ion source.     

Ambient Water-Stable Dianionic Electron Donors: Intramolecular Noncovalent Conduits Assist Charge Delocalization

Electron-rich π-conjugated dianions are known to be ambient unstable and their stabilization in ambient water is yet to be realized. We report the first example of an exceptionally stable naphthalenediimide-based dianion in ambient and hot water, forming one of the most stable redox-active dianion. The half-life (t_1/2) of dianion ( 1 a²⁻ ) is more than four months in ambient water. The dianionic state was confirmed by X-ray crystallography and by various spectroscopic methods. The noncovalent electronic conduits introduced for the first time in dianions, embrace n_O→π*_C≡N interactions and aid in delocalizing the dianionic charge as validated from theoretical studies. The dianions harness strong NIR absorption and electron donor ability to organic acceptors and metal ions, which make them suitable for potential green energy applications.     

Control of stereoselective protonation of enols1,2

A decalyl framework with a siloxy enolic moiety and proximate proton transferring groups was synthesized. On enolate generation with fluoride two competitive reaction modes were possible: (a) intermolecular protonation, and (b) intramolecular proton transfer by the proximate group. Control of the protonation stereochemistry proved possible by varying the proximate group and by changing the acidity of the medium. With the groups -CH2OH, -CH=O, and -CH2OCH2OCH3 as the proximate groups, only intermolecular proton transfer was observed with no dependence on acidity. In contrast, with -COO- and COOH, only intramolecular protonation resulted but again with no dependence on acidity of the medium. In contrast, with -CH2NH2 as the proximate group, intramolecular proton transfer predominated with a dependence on the effective pH of the medium. A kinetic analysis provided a linear-log relationship of the ratio of the two stereoisomers with the medium acidity. The analysis revealed that two acetic acid molecules are involved in providing the proton to the enolate moiety. A theoretical analysis was developed paralleling the experimental results. In the ketonization transition state, the hybridization was shown to be close to sp2 hybridized at the alpha-enolate carbon.     

Functionalization of substituted 2(1H)- and 4(1H)-pyridones. III. The preparation of substituted 6-Vinyl-1,2-dihydro-2-oxo- and 1,4-dihydro-4-oxo-3-pyridinecarboxylic acids through the chemistry of pyridone dianions

The synthesis of various substituted 6-vinyl-1,2-dihydro-2-oxo-3-pyridinecarboxylic acids from the dianions of 1,2-dihydro-6-methyl-2-oxo-3-pyridinecarbonitrile and the corresponding 3-t-butyl ester is reported. The dianions were generated with LDA in THF at low temperature and reacted with various carbonyl substrates. Several conditions for the dehydration and hydrolysis of these adducts to the vinyl pyridone acids are discussed. Employing the conditions used for the 2-pyridone analogs, a series of substituted 6-vinyl-1,4-di-hydro-4-oxo-3-pyridinecarboxylic acids was prepared through the new dianion of 1,4-dihydro-6-methyl-4-oxo-3-pyridinecarboxylic acid, t-butyl ester.     

Synthesis, structure, magnetic properties and DFT calculations of two hydroxo-bridged complexes based on Mn(III)(Schiff-Bases)

Two hydroxo-bridged complexes, {[Mn(III)(3-CH(3)O)salen](2)[Cr(III)(salen)(OH)(2)]}ClO(4)·6H(2)O (1) and {[Mn(III)(5-CH(3))salen](2)(OH)}ClO(4)·3H(2)O (2) [salen = N,N'-ethylenebis(salicylideneiminato) dianion], have been synthesized by the hydrolysis of the corresponding Mn(III)(Schiff-Bases) derivatives and [Cr(salen)(H(2)O)(2)]Cl precursors. X-Ray structure characterization reveals the discrete linear arched trinuclear structure of 1 and the 1D chain arrangement of 2. Magnetic experimental data and density functional theory (DFT) calculations both indicate the dominant antiferromagnetic interaction mediated by the hydroxo-bridges in both 1 and 2. Frequency-dependent AC susceptibilities reveal slow relaxation of 1 in low temperature. It is worth noting that the structure and magnetic properties of 1 is comparable to a reported cyano-bridged SMM, K[(5-Brsalen)(2)(H(2)O)(2)Mn(2)Cr(CN)(6)]·2H(2)O.     

Reaction and characterization of thioamide dianions derived from N-benzyl thioamides

Thioamide dianions were generated by the highly efficient reaction of N-benzyl thioamides with 2 equiv of BuLi. Alkylation, allylation, and silylation took place selectively at the carbon atom adjacent to the nitrogen atom of the thioamide dianions. Oxiranes and an aldehyde were also used as electrophiles in the reaction of thioamide dianions to form N-thioacyl 1,3- or 1,2-amino alcohols. The insertion reaction of elemental sulfur to a thioamide dianion and subsequent ethylation afforded a N-thioacyl hemithioaminal. NMR studies on the thioamide mono- and dianions derived from N-benzyl 2-methoxythiobenzamide showed a linear relationship between the chemical shifts of all carbon atoms of thioamide mono- and dianions. The results also suggested that the negative charge at the benzylic carbon atom of the dianion is not fully delocalized. The charge distribution patterns of the dianion are consistent with those of pi polarization.     

Conformational effects on photophysical characteristics of C5-C5'-linked dihydrothymine dimers in solution

Photophysical characteristics of N-substituted C5-C5'-linked dihydrothymine dimers (1a,b[meso], meso compounds of [5R,5'S]-bi-5,6-dihydrothymines; 1a,b[rac], racemic compounds of [5R,5'R]-bi-5,6-dihydrothymines and [5S,5'S]-bi-5,6-dihydrothymines) in aqueous solution with varying contents of less-polar aprotic solvent such as tetrahydrofuran or dioxane have been investigated by UV-absorption, and steady-state and time-resolved fluorescence spectroscopies. Among the C5-C5'-linked dimers, (5R,5'S)-bi-5,6-dihydro-1-methylthymine (1a[meso]) showed a red-shifted weak UV-absorption band at 270-350 nm and excimer fluorescence emission at lambda max = 370 nm with a quantum yield (phi F) of approximately 0.1 in phosphate buffer (pH < 10) at 293 K. Racemic compound of 5,6-dihydro-1-methylthymine dimer (1a[rac]), meso and racemic compounds of 5,6-dihydro-1,3-dimethylthymine dimers (1b[meso] and 1b[rac]) in phosphate buffer were nonfluorescent under similar conditions. The UV-absorption and fluorescence spectral characteristics of 1a[meso] in aqueous solution were interpreted in terms of intramolecular stacking interactions between the dihydropyrimidine chromophores leading to a preferential "closed-shell" conformation both in the ground state and the excited singlet state. In basic solutions at pH > pKa = 11.7, the fluorescence quantum yield of 1a[meso] decreased due to a dominant "open-shell" conformation resulting from the electrostatic repulsion between the deprotonated dihydrothymine chromophores of 1a[meso] in a dianion form.     

The chemistry of terpenes—VIII: Characterisation of the bisulphite adducts of α,β-unsaturated aldehydes by NMR spectroscopy

The NMR spectra of a series of sodium alkane-1-sulphonates and sodium 1-hydroxyalkane-1-sulphonates show that the two systems may be characterised by the -CH₂SO₃^- and -CH(OH)SO₃^? resonance signals at δ=ca. 2.85 and ca 4.4 ppm, respectively. Analysis of the NMR spectra of the bisulphite adducts formed by α,β-unsaturated aldehydes confirms the earlier structural assignments of the 1,3-disulphonic acid salts. The NMR spectra of the 1:1, 1:2, and 1:3 citral: bisulphite adducts indicate that the 1:2 adduct is disodium 1-oxo-3,7-dimethyloctane-3,6-disulphonate and not the 3,7-disulphonate as reported by previous workers. The acid-catalysed $\text{H}\text{D}$ exchange of 1-hydroxyalkane-1-sulphonates at the C-2 atom has been examined.     

The reductive metalation of 9-phenylacridine

The reductive metalation of 9-phenylacridine by sodium to a dianion is described and the reactions of the dianion with electrophiles investigated. Reactions of the dianion with methanol, dimethyl sulfate, X(CH₂)_nX (n = 2,3,4, X = Cl, Br), and methyl chloroformate were studied. Reactions occurred exclusively at the 9 and 10 positions forming 9,10-dihydro-9-phenylacridine derivatives. Of particular interest was the fact that the dianion was dialkylated with 1,2-dichloroethane but monoalkylated at the 9-position with 1,3-dichloropropane and 1,4-dichlorobutane. These results are compared to those obtained with dianions derived from other heterocyclic systems and analyzed using Baldwin's Rules for Ring Closure.     

An experimental and theoretical vibrational spectroscopic study of [AsPh(4)](2)[Sn(dmit)(3)] x Me(2)CO

As shown previously by X-ray structure determinations, [tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate(IV)](2-) salts, [Q](2)[Sn(dmit)(3)], contain isolated cations and dianions. While the tin centres generally having octahedral geometries, the overall shapes of the dianions of these complexes in the solid state can differ with conformations varying from T, Y to asymmetrical arrangements. We now report, as a follow up to our earlier study on the Y-shaped complex, [NEt(4)](2)[Sn(dmit)(3)], an experimental and theoretical study of the vibrational spectra of solid solvated {[AsPh(4)](2)[Sn(dmit)(3)] x Me(2)CO}, in which the dianion has a T-shaped conformation. The infrared and Raman spectra, recorded from 4000 to 150 cm(-1), have been analysed by different ab initio calculations based on restricted Hartree-Fock (RHF) and density functional theory (DFT-Beck3LYP). The calculations were carried out on isolated dianions and cations with the 6-31G and 6-31G(d) basis sets and effective core potentials of Steven, Bash and Krauss (SBK). Fundamentals, overtones and combinations have been assigned. Generally, the Y- and T-shaped dianions exhibit similar infrared/Raman spectra, apart from differences in the C=C and the symmetrical M-S stretching frequencies: such differences can be used diagnostically to distinguish the overall shape of the tris(chelated)metallate dianion.     

Molecular structure and vibrational spectra of phenolphthalein and its dianion

Infrared (IR) and Raman spectra of phenolphthalein (PP) and its dianion form (sodium and potassium salts) were studied both in the solid state and in aqueous solution. Band assignments were carried out on the basis of the isotope shifts of the ring deuterated and 13C-substituted derivatives. Spectral analyses reveal that the PP dianion exists as mixtures of the benzenoid form (colorless) and the quinonoid form (colored) in the solid state and in aqueous solution, while the neutral PP solely takes the gamma-lactone form. This work provides the first vibrational spectroscopic evidence for the coexistence of the two species in the PP dianions.     

A joined theoretical-experimental investigation on the 1H and 13C NMR signatures of defects in poly(vinyl chloride)

1H and 13C chemical shifts of PVC chains have been evaluated using quantum chemistry methods in order to evidence and interpret the NMR signatures of chains bearing unsaturated and branched defects. The geometrical structures of the stable conformers have been determined using molecular mechanics and the OPLS force field and then density functional theory with the B3LYP functional and the 6-311G(d) basis set. The nuclear shielding tensor has been calculated at the coupled-perturbed Kohn-Sham level (B3LYP exchange-correlation functional) using the 6-311+G(2d,p) basis set. The computational scheme accounts for the large number of stable conformers of the PVC chains, and average chemical shifts are evaluated using the Maxwell-Boltzmann distribution. Moreover, the chemical shifts are corrected for the inherent and rather systematic errors of the method of calculation by employing linear regression equations, which have been deduced from comparing experimental and theoretical results on small alkane model compounds containing Cl atoms and/or unsaturations. For each type of defect, PVC segments presenting different tacticities have been considered because it is known from linear PVC chains that the racemic (meso) dyads are characterized by larger (smaller) chemical shifts. NMR signatures of unsaturations in PVC chains have been highlighted for the internal -CH=CH- and -CH=CCl- units as well as for terminal unsaturations like the chloroallylic -CH=CH-CH2Cl group. In particular, the 13C chemical shifts of the two sp2 C atoms are very close for the chloroallylic end group. The CH2 and CHCl units surrounding an unsaturation present also specific 13C chemical shifts, which allow distinguishing them from the others. In the case of the proton, the CH2 unit of the -CHCl-CH2-CCl=CH- segment presents a larger chemical shift (2.6-2.7 ppm), while some CHCl units close to the -CH=CH- unsaturations appear at rather small chemical shifts (3.7 ppm). The -CH2Cl and -CHCl-CH2Cl branches also display specific signatures, which result in large part from modifications of the equilibrium conformations and their reduced number owing to the increased steric interactions. These branches lead to the appearance of 13C peaks at lower field associated either to the CH unit linking the -CH2Cl and -CHCl-CH2Cl branches (50 ppm) or to the CHCl unit of the ethyl branches (60 ppm). The corresponding protons resonate also at specific frequencies: 3.5-4.0 ppm for the -CH2Cl branch or 3.8-4.2 ppm for the terminal unit of the -CHCl-CH2Cl branch. Several of these signatures have been detected in the experimental 1H and 13C NMR spectra and are consistent with the reaction mechanisms.     

Infrared spectra and structure of carbanions : XIII. Dimeric dianions derived from α,β-diaryl-acrylonitriles

The IR spectra of the products of electrochemical and chemical (alkali metals, naphthalene anion-radical) reduction of substituted α,βdiaryl-acrylonitriles (32 compounds) were studied. It was found that the anion-radicals initially formed dimerize into the corresponding dimeric dianions. Correlation of v(CN) (dimeric dianions) with v(CN) (sodium methoxide adducts, ref 26), as well as with the σ^? constants of the substituents in the α-aromatic rings were found. The effects of the β-substituents, counter ions and solvents on v(CN) of the dimeric dianions are discussed.