Viscoelasticity and birefringence of polyisoprene

The complex Young's modulus, E^*(ω), and the complex strain-optical coefficient, O^*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ～ 130 Hz and a temperature range of 22 ～ ?100°C. The imaginary part of O^*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O^* could be understood by the assumption that E^* = E_R^* + E_G^* and O^* = C_RE_R^* + C_GE_G^*, where E_R^* and E_G^* were complex quantities and C_R and C_G were constants. The C_R value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10^?9 Pa^?1. The C_G value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10^?11 Pa^?1. The E_G^*, which was the major component of E^* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The E_R^*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the E_G^* was stronger than that of the E_R^*. This difference caused the breakdown of the thermorheological simplicity for E^* and O^* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc.     

Elastic modulus of the crystalline phase of poly(cis 1,4-isoprene)

The crystalline elastic modulus of poly(cis 1,4-isoprene) has been measured by x rays and calculated by molecular mechanics. The experimental modulus is E = (2.3 ± 0.3) × 10⁹N m^?2. The calculated modulus is E = (8.8 ± 0.1) × 10⁹N m^?2 for chains in S⁺ cis S^?T conformation and E = (6.1 ± 0.1) × 10⁹N m^?2 for chains in S⁺ cis S+T conformation. The modulus calculated for a statistical structure including both conformation is E = (6.7 ± 0.1) × 10⁹N m^?2. The experimental modulus is thought to be a lower limit because of partial crystallinity of the sample. The chief mechanism of deformation is rotation around single bonds adjacent to the double bond.     

INDO calculations of the solvent dependence of some spin–spin couplings of fluorocarbons

The results of some SCPT and SOS calculations of ¹J(CH), ¹J(FC), ²J(FH), ³J(FH), ³J(FF) and ¹J(CC) in a variety of solvents are reported. The calculations employ the solvaton model and INDO parameters. In almost all cases the coupling is predicted to increase as the dielectric constant of the solvent increases, the exception being ³J(FH)cis in trifluoroethylene which is supported by experimental results.     

Thermodynamics of mixtures of hexane and heptane isomers with normal and branched hexadecane

Molar excess mixing enthalpies h ^E , Gibbs free energies g ^E and hence entropies s ^E have been obtained using calorimetry and the vapor sorption method at 25°C for hexane isomers+2,2,4,4,6,8,8-heptamethylnonane, a highly branched C ₁₆ . The h ^E and g ^E are negative while Ts ^E are positive, but small. The values are explained by the Prigogine-Flory theory through negative free volume contributions to h ^E and Ts ^E , counterbalanced in the case of Ts ^E by the positive combinatiorial Ts ^E for mixing molecules of different size. No contribution is seen from the interaction between methyl and methylene groups. The excess quantities are also obtained for hexane and heptane isomers mixed with n-hexadecane. Values of h ^E and Ts ^E are now strongly positive, while those of g ^E are only slightly less negative. The interpretation requires two recently advanced contributions in addition to those of the Prigogine-Flory theory: 1) a decrease of order when correlations of orientations between n-C ₁₆ molecules in the pure liquid are replaced in the solution by weaker correlations whose strengths depend on the shapes of the lower alkane isomers. For lower alkane isomers of the same shape, but highly sterically hindered, h ^E and Ts ^E are small, manifesting, 2) a negative contribution, ascribed to a rotational ordering of n-C ₁₆ segments on the sterically-hindered molecule. Enthalpy-entropy compensation is observed for these new contributions, arising from their rapid fall-off with increase of temperature.     

Synthesis and Spectroscopic Characterization of Two Different Types of Heterobimetallic Glycolate Complexes of Niobium(V)

An entirely new class of heterobimetallic homoleptic glycolate complexes of the type Nb(OGO)₃{Ta(OGO)₂} [where G=CMe₂CH₂CH₂CMe₂ (G¹) (3); CMe₂CH₂ CHMe(G²) (4); CHMeCHMe (G³) (5); CH₂CMe₂CH₂ (G⁴) (6); CMe₂CMe₂(G⁵) (7); CH₂CHMeCH₂ (G⁶) (8); CH₂CEt₂CH₂ (G⁷) (9); CH₂CMe(Prⁿ)CH₂ (G⁸) (10)] have been prepared by the reactions of Nb(OGO)₂(OGOH) [G=G¹ (1a); G² (1b); G³ (1c); G⁴ (1d); G⁵ (1e); G⁶ (1f); G⁷ (1g); G⁸ (1h)] with Ta(OGO)₂ (OPrⁱ) (G=G¹ (2a); G² (2b); G³ (2c); G⁴ (2d); G⁵ (2e) G⁶ (2f); G⁷ (2g); G⁸ (2h). In addition to the novel derivatives (2)–(10), our earlier investigations on heterobimetallic glycolate-alkoxide derivatives have been extended to derivatives of the type Nb(OGO) [where M=A1 n=3, G=G³ (11);G⁴ (12); G⁶ (13) G⁷ (14); G^s (15); G⁹=CH₂CH₂CH₂ (16) and M=Ti (n=4, G=G⁴) (17), Zr(n=4,G=G⁴) (18)], which are conveniently prepared by the reactions of metalloligands Nb(OGO)₂(OGOH) [G=G³ (1c); G⁴ (1d); G⁶ (1f); G⁷ (1g); G⁸ (1h); G⁹ (1i)] with different metal alkoxides. All of these new complexes have been characterized by elemental analyses, molecular weight determinations, and spectroscopic (I.r. and ¹H, ²⁷Al-n.m.r.) studies. Structural features of the new derivatives have been elucidated on the basis of molecular weight and spectroscopic data.     

Precision measurement of the energy of the 4d 9 5s 2 2 D 5/2 metastable level in Ag I

The energy of the 4d ⁹ 5s ^{2 2} D _5/2 metastable level in Ag I, which is the upper level of the very narrow 5s ² S _1/2 – 4d ⁹ 5s ^{2 2} D _5/2 two-photon transition at 661.2 nm, has been determined from precision measurements of the wavelengths of the 206.1 nm (5s ² S _1/2 – 6p ² P ₃ ^2/0 ) and 547.5 nm (4d ⁹ 5s ^{2 2} D _5/2 – 6p ² P ₃ ^2/0 ) lines emitted from a hollow-cathode discharge. The measured energy of the 4d ⁹ 5s ^{2 2} D _5/2 level, 30 242.286(7) cm^–1, is combined with the known hyperfine splittings and the estimated¹⁰⁷Ag-¹⁰⁹Ag isotope shift to obtain accurate absolute frequencies for the hyperfine components of the 661.2 nm transition. These results should help in the detection of the narrow 661.2 nm two-photon transition, which has been proposed as a new optical frequency standard.     

A Closed-Form Relation for Dimension-Dependent Two-Electron Matrix Elements of the Interelectronic Distance

The evaluation of matrix elements of two electron atoms is fundamental for the study of the electronic properties of those systems. We add to this knowledge by presenting an explicit expression for the matrix elements of the inverse of the interelectronic distance of two-electron atoms in any spatial dimension D. The basis functions used are the D-dependent hydrogenic wavefunctions {1s ²,2p ²,3d ²,4f ²,5g ²,...,21y ²,...}, extending and including, in this way, the results of the previous basis set {1s ²,2p ²,3d ²,4f ²}. The methodology used does not employ Fourier integral transforms as in previous works but hypergeometric transformation formulas.     

Cubic phases of 4′-n-alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC-n)

The structure of the thermotropic cubic phases of 4′- ⁿ -alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC- ⁿ , where ⁿ indicates the number of carbon atoms in the alkoxy group) was studied by X-ray diffraction. For the homologues with ⁿ = 15, 16, 17, and 18, the cubic phase was of an ^Ia 3 ^d type, whereas the homologues with ⁿ = 19, 20, and 21 exhibited an ^Im 3 ^m cubic structure; for these seven homologues the same type of cubic structure was observed both on heating and cooling. Further lengthening of the alkoxy chain to ⁿ = 22 and 26, however, gave two types of cubic structure in the cubic phase region on heating, one with ^Im 3 ^m symmetry in the low temperature region and the other with ^Ia 3 ^d symmetry in the high temperature region. On cooling, the two homologues exhibited the ^Ia 3 ^d cubic structure only. This is the first example in the cubic phase region of a series of homologues containing two types of structure, dependent on temperature and ⁿ . Such a complicated phase diagram in the cubic region is clearly understood qualitatively in terms of Gibbs free energy-temperature diagrams. The dependence of structural parameters such as the cubic lattice constant on the alkoxy chain length ⁿ are also presented and discussed.     

The collisional quenching of electronically excited arsenic atoms As(42DJ) and As(42PJ), studied by time-resolved attenuation of atomic resonance radiation

A kinetic investigation of electronically excited arsenic atoms in the low-lying states, As(4p^{3 2}D_J) and As(4p^{3 2}P_J), ca. 1.33 and 2.28 eV, respectively, above the 4⁴S_3/2 ground state, has been carried out by atomic absorption spectroscopy. Atoms in these optically metastable states were generated by the pulsed irradiation of suitable arsenic compounds (AsMe₃ for ²D and AsCl₃ for ²P) in different spectral regions and monitored photoelectrically by time-resolved attenuation of atomic resonance radiation. Rate constants for the deactivation of these two states are reported for a range of collision partners. The data are compared with those of the analogous states of lighter atoms in group V, namely, P(3²D_J, 3²P_J) and N(2²D_J, 2²P_J), and discussed in terms of spin and orbital symmetry considerations.     

Nuclear model calculation for cyclotron production of 61Cu as a PET imaging

⁶¹Cu is positron emitter and can be used as the PET and molecular imaging. In this study cyclotron production of ⁶¹Cu via ⁶¹Ni(p,n)⁶¹Cu, ^natNi(p,x)⁶¹Cu, ^natNi(d,x)⁶¹Cu, ^natNi(α,x)⁶¹Cu, ^natZn(p,x)⁶¹Cu and ⁵⁹Co(α,2n)⁶¹Cu reactions was investigated. The ALICE/ASH (hybrid and GDH models) and TALYS-1.2 codes were used to calculate excitation functions for proton, alpha and deuteron induced on ^natNi, proton on ⁶¹Ni and ^natZn and also alpha-particle on ⁵⁹Co targets that lead to the production of ⁶¹Cu radioisotopes using intermediate energy accelerators. In addition, we compared the data obtained from in this study with the reported measurement by experimental data. Moreover, optimal thickness of the targets and physical yield were obtained by stopping and range of ions in matter code for each reaction. Eventually ⁶¹Ni(p,n)⁶¹Cu and ⁵⁹Co(α,2n)⁶¹Cu reaction to produce ⁶¹Cu in no-carrier added state with high production yield was suggested. Finally the ^natNi(p,x)⁶¹Cu reaction was employed to test the target preparation using electroplating technique.     

Preparation and X-ray structures of complexes of 18-membered crown ethers with polyfunctional guests: Urea and (O-alkyliso)uronium salts

The preparation and X-ray structure determinations of six complexes of urea and (O-n-butyliso)uronium salts with crown ethers are presented. Urea forms isostructural 5:1 adducts with 18-crown-6 (1) and aza-18-crown-6 (2), in which two urea molecules are each hydrogen bonded to two neighbouring hetero atoms of the macroring. The remaining urea molecules form two-dimensional layers alternating with crown ether layers. In both complexes the macroring has theg ⁺ g ⁺ a ag ^– a ag ^– a g ^– g ^– a ag ⁺ a ag ⁺ a conformation withC _i symmetry. In the solid 1:1 complex of O-n-butylisouronium picrate with 18-crown-6 (3) two types of conformations of the macroring were observed: theg ⁺ g ⁺ a ag ^– a ag ⁺ a ag ^– g ^– ag ^– a ag ⁺ a conformation with approximateC _m symmetry and to a lesser extent theg ⁺ g ⁺ a ag ^– a ag ⁺ a g ⁺ g ⁺ a ag ^– a ag ⁺ a conformation with approximateC ₂ symmetry. Both conformations allow the guest to form three hydrogen bonds to the macrocyclic host. Three complexes of 18-crown-6 and uronium salts have been prepared and characterized by X-ray crystallography. The 1:1 complexes with uronium nitrate (4) and uronium picrate (5) both exhibit the sameC ₂ conformation and the same hydrogen bonding scheme as in the least occupied form of the previous complex. A 1:2 complex with uroniump-toluenesulphonate (6) has a different hydrogen bonding scheme (two hydrogen bonds per cation to neighbouring oxygen atoms of the macroring) and a different conformation of the host molecule (theag ⁺ a ag ^– a ag ⁺ a ag ^– a ag ⁺ a ag ^– a conformation with almostD _3d symmetry). An attempt to prepare a solid uronium nitrate complex with diaza-18-crown-6 in the same way as the 18-crown-6·uronium nitrate (1:1) complex did not yield the expected result. Instead X-ray analysis revealed that the uronium ion is dissociated, resulting in the nitrate salt of the diprotonated diaza crown ether (7). Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82058 (26 pages).     

The atomic states of nickel

The Ni 3d ⁹ 4s ¹(³ D)–3d ¹⁰(¹ S) and 3d ⁹ 4s ¹(³ D)-3d ⁸4s ²(³ F) atomic excitation energies have been computed using large multireference CI wave functions in conjunction with a large ANO basis set. Radial correlation effects in the 3d shell are found to be very important and are included using CASSCF wave functions having the 3d and correlating 3d orbitals in the active space. The previous discrepancy (0.5 eV) with experiment for the ³ D–¹ S excitation is reduced to 0.1 eV when the 3d3d references are included in the CI. For the ³ F state, the 4s-4p near degeneracy gives rise to important 4s ²4p ² excitations in addition to the 3d3d excitations which are important for the ³ D and ¹ S states. Inclusion of only 3d-3d correlation in the ³ F and ³ D CI reference spaces yields a ³ F–³ D separation which is in error by 0.12 eV. Addition of the 4s ²4p ² excitations to the ³ F reference space is estimated to increase the discrepancy with experiment by an additional 0.1 eV.     

Effect of the exchange integral K2s2p on the 2p-orbitals of the 1P and 3P states of the beryllium isoelectronic sequence arising from the configuration (1s)2(2s)(2p)

The ¹P and ³P states arising from the configuration (1s)²(2s)(2p) of the Be isoelectronic sequence are investigated. In the single configuration approximation, the energies of the two states are expressed as E⁰ + K_2s2p and E⁰ - K_2s2p, respectively. K_2s2p is the exchange integral between the 2s and 2p electrons and E⁰ is the energy of a model in which K_2s2p is deleted. First we calculate the 2s- and 2p-orbitals in this model. Second, by taking account of K_2s2p in this model, effects of this term on the 2p-orbitals in the ^1,3P states are investigated. In this manner, an explanation is given for the following facts which are obtained from a minimal Slater-type orbital set; (1) for Be and B⁺, the 2p-orbital of the ¹P state is broader than that of the ³P state; (2) for C²⁺, the extension of the 2p-orbital in the two states is almost the same; (3) for O⁴⁺ and Ne⁶⁺, in contrast to Be and B⁺, the 2p-orbital of the ¹P state is tighter than that of the ³P state.     

2-甲基-2-丁醇的低温热容和热力学性质

本文用精密自动绝热量热仪测定了2-甲基-2-丁醇在80～305 K温区的热容,从热容曲线(Cp-T) 发现三个固－固相变和一个固－液相变, 其相变温度分别为T = 146.355, 149.929, 214.395, 262.706 K。从实验热容数据用最小二乘法得到以下四个温区的热容拟合方程。在80～140K温区, Cp,m = 39.208 + 8.0724X - 1.9583X2 + 10.06X3 + 1.799X4 - 7.2778X5 + 1.4919X6, 折合温度X = (T –110) / 30; 在 155 ～ 210 K温区, Cp,m = 70.701 + 10.631X + 12.767X2 + 0.3583X3 - 22.272X4 - 0.417X5 + 12.055X6, X = (T –182.5) /27.5; 在220 ～ 250 K温区, Cp,m = 99.176 + 7.7199X - 26.138X2 + 28.949X3 + 0.7599X4 - 25.823X5 + 21.131X6, X = (T – 235)/15; 在 270～305 K温区, Cp,m =121.73 + 16.53 X- 1.0732X2 - 34.937X3 - 19.865X4 + 24.324X5 + 18.544X6, X = (T –287.5)/17.5。从实验热容计算出相变焓分别为0.9392, 1.541, 0.6646, 2.239 kJ×mol-1; 相变熵分别为6.417, 10.28, 3.100, 8.527 J×K-1×mol-1。根据热力学函数关系式计算出80～305 K温区每隔5 K的热力学函数值 [HT –H298.15]和 [ST –S298.15]。     

13C NMR spectra of 2,3-dihydro-1H-benzo[b]azepines: Differentiation of diastereomers

The ¹³C NMR spectra of 23 2,3-dihydro-1H-benzo[b]azepines, including nine pairs of diastereomers separated by chromatography, [(2R*, 3R^*) and (2R^*), 3S^*)] are hereby assigned and discussed. The relative configurations of the diastereomers were assigned by two methods. The first, based on the chemical shifts of the asymmetric carbons C-2 and C-3 (with regression analysis), shows that the values for (R^*, R^*) are approximately 1 ppm lower than those for (R^*, S^*) diastereomers. The second method uses the chemical shifts, δ₃, of the R₃(CH₃) substituents. When these δ₃ values are compared by means of the δ₃-δ_m difference (δ_m is the mean value obtained from compounds where R₂=H), the difference is always negative for (R^*, R^*) and positive for (R^*, S^*). This is attributed to a γ-gauche effect between R₂ and R₃ in the case of (R^*, R^*) diastereomers (R₂ and R₃ are cis). The results corroborate those already obtained by ¹H NMR [J(23)(R^*, R^*)<J(23)(R^*, S^*)] and are a confirmation of the results of a radiocrystallographic examination carried out on two nitrogen acetylated diastereomers.     

Molecular mechanics simulation studies of dienoic hydrocarbons: From alkenes to 1-Palmitoyl-2-linoleoyl-phosphatidylcholines

Although no crystal structures of mixed-chain phosphatidylcholines with unsaturated sn-2 acyl chains exist, the force field method in conjunction with the experimentally determined structure of saturated identical-chain phosphatidylcholine can be applied to simulate molecular structure for mixed-chain phosphatidylcholines. In this study, the packing models of mixed-chain 1-palmitoyl-2-linoleoyl-phosphatidylcholines in bilayers at temperatures below the gel-liquid crystalline phase transition temperature or T < T_m are simulated by using Allinger's MM3(92) force field. Our results indicate that the unsaturated sn-2 acyl chains of the mixed-chain lipid can fold into two energy-minimized topologies: the crankshaftlike and the U-shaped motifs. The folded region in the crankshiftlike sn-2 acyl chain is characterized by a sequence s⁻ Δs⁺s⁺Δs⁻, and the U-shaped chain arises from the characteristic sequence s⁻Δs⁺s⁻Δs⁺, where s^± denotes the ± skew conformation and Δ the cis carbon-carbon double bond. These modeled structures of 1-palmitoyl-2-linoleoyl-phosphatidylcholines in the bilayer at T < T_m should not be regarded as highly rigid structures, since torsion angles of carbon-carbon bonds associated with sequences s Δs⁺s⁺Δs and s Δs⁺s⁻Δ s⁺ can fluctuate somewhat without appreciably affecting the steric energy of the corresponding lipid bilayer. © 1996 by John Wiley & Sons, Inc.     

Thermodynamics of mixed-ligand complexation of yttrium group lanthanide ethylenediaminetetraacetates

Mixed-ligand complexation of yttrium subgroup lanthanide ethylenediaminetetraacetates with asparaginate, iminodiacetate, and nitrilotriacetate ions in aqueous solution was studied by calorimetry and pH-metry. The full set of thermodynamic parameters (logK, Δ _r G ₀, Δ _r H, Δ _r S) of the addition reactions of Asp²⁻, Ida²⁻, and Nta³⁻ to LnEdta⁻ (Ln³⁺ = Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺, Lu³⁺) was determined at 298.15 K and ionic strength I = 0.5(KNO₃). The change in the thermodynamic parameters of the reactions over the series of lanthanides was discussed.     

Theoretical study of low‐lying electronic states of the LiRb+ molecular ion: Structure,spectroscopy and transition dipole moments

The electronic structure and the spectroscopic properties for low‐lying electronic states of the LiRb⁺ molecular ion, dissociating into Li (2s, 2p, 3s, 3p, 3d, 4s, and 4p) + Rb⁺ and Li⁺ + Rb (5s, 5p, 4d, 6s, 6p, 5d, and 7s), have been investigated using an ab initio approach based on non‐empirical pseudo potentials for the Li and Rb cores and parametrized l‐dependent polarization potential. We have determined the adiabatic potential energy curves and their spectroscopic constants for many electronic states of ²Σ⁺, ²Π, and ²Δ symmetries. A satisfying agreement, for the spectroscopic constants, has been obtained for the ground and the first excited states with the available theoretical works. Potential energy curves were presented, for the first time, for the higher excited states. In addition, we have localised and analysed the avoided crossings between electronic states of ²Σ⁺ and ²Π symmetries. Their existences can be related to the interaction between the potential energy curves and to the charge transfer process between the two ionic systems Li⁺Rb and LiRb⁺. Moreover, we have determined the transition dipole moments from X²Σ⁺ and 2²Σ⁺ states to higher excited states of ²Σ⁺ and ²Π symmetries. For our best knowledge, no experimental data on the LiRb⁺ molecular ion is available. These theoretical data can help experimentalists to optimize photoassociative formation of ultracold LiRb⁺ molecular ion and their longevity in a trap or in an optical lattice. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Different coordination modes of trans‐2‐{[(2‐methoxyphenyl)imino]methyl}phenoxide in rare‐earth complexes: influence of the metal cation radius and the number of ligands on steric congestion and ligand coordination modes

A simple and effective synthetic route to homo‐ and heteroleptic rare‐earth (Ln = Y, La and Nd) complexes with a tridentate Schiff base anion has been demonstrated using exchange reactions of rare‐earth chlorides with in‐situ‐generated sodium (E)‐2‐{[(2‐methoxyphenyl)imino]methyl}phenoxide in different molar ratios in absolute methanol. Five crystal structures have been determined and studied, namely tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐κ³O¹,N,O²)lanthanum, [La(C₁₄H₁₂NO₂)₃], ( 1 ), tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐κ³O¹,N,O²)neodymium tetrahydrofuran disolvate, [La(C₁₄H₁₂NO₂)₃]·2C₄H₈O, ( 2 )·2THF, tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato)‐κ³O¹,N,O²;κ³O¹,N,O²;κ²N,O¹‐yttrium, [Y(C₁₄H₁₂NO₂)₃], ( 3 ), dichlorido‐1κCl,2κCl‐μ‐methanolato‐1:2κ²O:O‐methanol‐2κO‐(μ‐2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐1κ³O¹,N,O²:2κO¹)bis(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato)‐1κ³O¹,N,O²;2κ³O¹,N,O²‐diyttrium–tetrahydrofuran–methanol (1/1/1), [Y₂(C₁₄H₁₂NO₂)₃(CH₃O)Cl₂(CH₄O)]·CH₄O·C₄H₈O, ( 4 )·MeOH·THF, and bis(μ‐2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐1κ³O¹,N,O²:2κO¹)bis(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐2κ³O¹,N,O²)sodiumyttrium chloroform disolvate, [NaY(C₁₄H₁₂NO₂)₄]·2CHCl₃, ( 5 )·2CHCl₃. Structural peculiarities of homoleptic tris(iminophenoxide)s ( 1 )–( 3 ), binuclear tris(iminophenoxide) ( 4 ) and homoleptic ate tetrakis(iminophenoxide) ( 5 ) are discussed. The nonflat Schiff base ligand displays μ₂‐κ³O¹,N,O²:κO¹ bridging, and κ³O¹,N,O² and κ²N,O¹ terminal coordination modes, depending on steric congestion, which in turn depends on the ionic radii of the rare‐earth metals and the number of coordinated ligands. It has been demonstrated that interligand dihedral angles of the phenoxide ligand are convenient for comparing steric hindrance in complexes. ( 4 )·MeOH has a flat Y₂O₂ rhomboid core and exhibits both inter‐ and intramolecular MeO—H…Cl hydrogen bonding. Catalytic systems based on complexes ( 1 )–( 3 ) and ( 5 ) have demonstrated medium catalytic performance in acrylonitrile polymerization, providing polyacrylonitrile samples with narrow polydispersity.     

The kinetics and mechanisms of gas phase elimination of primary,secondary, and tertiary 2‐hydroxyalkylbenzenes

2‐Phenylethanol, racemic 1‐phenyl‐2‐propanol, and 2‐methyl‐1‐phenyl‐2‐propanol have been pyrolyzed in a static system over the temperature range 449.3–490.6°C and pressure range 65–198 torr. The decomposition reactions of these alcohols in seasoned vessels are homogeneous, unimolecular, and follow a first‐order rate law. The Arrhenius equations for the overall decomposition and partial rates of products formation were found as follows: for 2‐phenylethanol, overall rate log k₁(s⁻¹)=12.43−228.1 kJ mol⁻¹ (2.303 RT)⁻¹, toluene formation log k₁(s⁻¹)=12.97−249.2 kJ mol⁻¹ (2.303 RT)⁻¹, styrene formation log k₁(s⁻¹)=12.40−229.2 kJ mol⁻¹(2.303 RT)⁻¹, ethylbenzene formation log k₁(s⁻¹)=12.96−253.2 kJ mol⁻¹(2.303 RT)⁻¹; for 1‐phenyl‐2‐propanol, overall rate log k₁(s⁻¹)=13.03−233.5 kJ mol⁻¹(2.303 RT)⁻¹, toluene formation log k₁(s⁻¹)=13.04−240.1 kJ mol⁻¹(2.303 RT)⁻¹, unsaturated hydrocarbons+indene formation log k₁(s⁻¹)=12.19−224.3 kJ mol⁻¹(2.303 RT)⁻¹; for 2‐methyl‐1‐phenyl‐2‐propanol, overall rate log k₁(s⁻¹)=12.68−222.1 kJ mol⁻¹(2.303 RT)⁻¹, toluene formation log k₁(s⁻¹)=12.65−222.9 kJ mol⁻¹(2.303 RT)⁻¹, phenylpropenes formation log k₁(s⁻¹)=12.27−226.2 kJ mol⁻¹(2.303 RT)⁻¹. The overall decomposition rates of the 2‐hydroxyalkylbenzenes show a small but significant increase from primary to tertiary alcohol reactant. Two competitive eliminations are shown by each of the substrates: the dehydration process tends to decrease in relative importance from the primary to the tertiary alcohol substrate, while toluene formation increases. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 401–407, 1999