Gas-phase reactions of atomic lanthanide cations with CO2 and CS2: room-temperature kinetics and periodicities in reactivity

Gas-phase reactions of atomic lanthanide cations (excluding Pm+) have been surveyed systematically with CO2 and CS2 using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Observations are reported for reactions with La+, Ce+, Pr+, Nd+, Sm+, Eu+, Gd+, Tb+, Dy+, Ho+, Er+, Tm+, Yb+, and Lu+ at room temperature (295 +/- 2 K) in helium at a total pressure of 0.35 +/- 0.02 Torr. The observed primary reaction channels correspond to X-atom transfer (X = O, S) and CX2 addition. X-atom transfer is the predominant reaction channel with La+, Ce+, Pr+, Nd+, Gd+, Tb+, and Lu+, and CX2 addition occurs with the other lanthanide cations. Competition between these two channels is seen only in the reactions of CS2 with Nd+ and Lu+. Rate coefficient measurements indicate a periodicity in the reaction efficiencies of the early and late lanthanides. With CO2 the observed trends in reactivity across the row and with exothermicity follow trends in the energy required to achieve two unpaired non-f valence electrons by electron promotion within the Ln+ cation that suggest the presence of a kinetic barrier, in a manner much like those observed previously for reactions with isoelectronic N2O. In contrast, no such barrier is evident for S-atom transfer from the valence isolectronic CS2 molecule which proceeds at unit efficiency, and this is attributed to the much higher polarizability of CS2 compared to CO2 and N2O. Up to five CX2 molecules were observed to add sequentially to selected Ln+ and LnX+ cations.     

Reactions of methyl fluoride with atomic transition-metal and main-group cations: gas-phase room-temperature kinetics and periodicities in reactivity

Reactions of CH(3)F have been surveyed systematically at room temperature with 46 different atomic cations using an inductively coupled plasma/selected-ion flow tube tandem mass spectrometer. Rate coefficients and product distributions were measured for the reactions of fourth-period atomic ions from K(+) to Se(+), of fifth-period atomic ions from Rb(+) to Te(+) (excluding Tc(+)), and of sixth-period atomic ions from Cs(+) to Bi(+). Primary reaction channels were observed corresponding to F atom transfer, CH(3)F addition, HF elimination, and H(2) elimination. The early-transition-metal cations exhibit a much more active chemistry than the late-transition-metal cations, and there are periodic features in the chemical activity and reaction efficiency that maximize with Ti(+), As(+), Y(+), Hf(+), and Pt(+). F atom transfer appears to be thermodynamically controlled, although a periodic variation in efficiency is observed within the early-transition-metal cations which maximizes with Ti(+), Y(+), and Hf(+). Addition of CH(3)F was observed exclusively (>99%) with the late-fourth-period cations from Mn(+) to Ga(+), the fifth-period cations from Ru(+) to Te(+), and the sixth-period cations from Hg(+) to Bi(+) as well as Re(+). Periodic trends are observed in the effective bimolecular rate coefficient for CH(3)F addition, and these are consistent with expected trends in the electrostatic binding energies of the adduct ions and measured trends in the standard free energy of addition. HF elimination is the major reaction channel with As(+), while dehydrogenation dominates the reactions of W(+), Os(+), Ir(+), and Pt(+). Sequential F atom transfer is observed with the early-transition-metal cations, with the number of F atoms transferred increasing across the periodic table from two to four, maximizing at four for the group 5 cations Nb(+)(d(4)) and Ta(+)(d(3)s(1)), and stopping at two with V(+)(d(4)). Sequential CH(3)F addition was observed with many atomic cations and all of the metal mono- and multifluoride cations that were formed.     

Carbon disulfide reactions with atomic transition-metal and main-group cations: gas-phase room-temperature kinetics and periodicities in reactivity

The reactions of 46 atomic-metal cations with CS2 have been investigated at room temperature using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients and products were measured for the reactions of fourth-period atomic ions from K+ to Se+, of fifth-period atomic ions from Rb+ to Te+ (excluding Tc+), and of sixth-period atomic ions from Cs+ to Bi+. Primary reaction channels were observed leading to S-atom transfer, CS2 addition and, with Hg+, electron transfer. S-atom transfer appears to be thermodynamically controlled and occurs exclusively, and with unit efficiency, in the reactions with most early transition-metal cations (Sc+, Ti+, Y+, Zr+, Nb+, La+, Hf+, Ta+, and W+) and with several main-group cations (As+, Sb+) and less efficiently with Se+, Re+ and Os+. Other ions, including most late transition and main-group metal cations, react with CS2 with measurable rates mostly through CS2 addition or not at all (K+, Rb+, Cs+). Traces of excited states (< 10%) were seen from an inspection of the observed product ions to be involved in the reactions with Mo+, Te+, Ba+ and Au+ and possibly Pt+ and Ir+. The primary products YS+, ZrS+, NbS+, HfS+, TaS+, WS+, ReS+ and OsS+ react further by S-atom transfer to form MS2(+), and TaS2(+) reacts further to form TaS3(+). CS2 addition occurs with the cations MCS2(+), MS+, MS2(+), CS2(+), and TaS3(+) to form M+(CS2)(n) (n < or = 4), MS+(CS2)(n) (n < or = 4), MS2(+)(CS2)(n) (n < or = 3), (CS2)2(+) and TaS3(+)(CS2). Up to four CS2 molecules add sequentially to bare metal cations and monosulfide cations, and three to disulfide cations. Equilibrium constant measurements are reported that provide some insight into the standard free energy change for CS2 ligation. Periodic variations in deltaG degrees are as expected from the variation in electrostatic attraction, which follows the trend in atomic-ion size and the trend in repulsion between the orbitals of the atomic cations and the occupied orbitals of CS2.     

Enantiomerically Enriched Bicyclic Hydroxamic Acids in One Step from α-Aminohydroxamic Acids and Keto Acids via Cyclocondensation

New enantiomerically enriched bicyclic hydroxamic acids, 1-hydroxy-dihydro-1H-pyrrolo[1,2-a]imidazole-2,5(3H,6H)-diones, have been synthesized by the cyclocondensation of L-α-aminohydroxamic acids with keto acids in a highly chemo- and stereoselective manner. The cis configuration between the amino acid side chain and the methyl group at C7a in 1H-pyrrolo[1,2-a]imidazole-2,5-dione was unambiguously established by X-ray crystallographic analysis. This method could also be applied to the cyclocondensation with o-formylbenzoic acid, giving a tricyclic hydroxamic acid in a good yield.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

On-wafer thermomechanical characterization of a thin film polyimide formed by vapor deposition polymerization for through-silicon via applications: Comparison to plasma-enhanced chemical vapor deposition SiO2

Thin-film polyimides were prepared by solvent-less vapor deposition polymerization (VDP) from pyromellitic dianhydride and 4,4′-oxydianiline at 200 °C for liner dielectric formation of vertical interconnects called through-silicon vias (TSVs) used in three-dimensionally stacked integrated circuit (3DICs). FTIR, synchrotron XPS, and TDS were employed for determining the imidization ratio, and in addition, the mechanical properties, coefficient of thermal expansion and Young's modulus, of the VDP polyimide were characterized on Si wafers. The VDP polyimide exhibited extremely high conformality, beyond 75%, toward high-aspect-ratio deep Si holes, compared with conventional SiO₂ prepared by plasma-enhanced chemical vapor deposition. The adhesion between the VDP polyimide and Si wafer was enhanced by an Al-chelate promotor. Remarkably, the VDP polyimide TSV liner dielectrics showed much less thermomechanical stresses applied to the Si surrounding the TSVs than the plasma-chemical vapor deposition SiO₂. The small keep-out zone is expected for scaling down highly reliable 3DICs for the upcoming real artificial intelligence society.     

Two-dimensional high-performance liquid chromatographic determination of day–night variation of d-alanine in mammals and factors controlling the circadian changes

d-Alanine (d-Ala) is one of the naturally occurring d-amino acids in mammals, and its amount is known to have characteristic circadian changes. It is a candidate for a novel physiologically active substance and/or a biomarker, and the regulation mechanisms of the intrinsic amounts of d-Ala are expected to be clarified. In the present study, the effects of the possible factors controlling the d-Ala amounts, e.g., diet, d-amino acid oxidase (DAO) and intestinal bacteria, on the day–night changes in the intrinsic d-Ala amounts have been investigated using a highly sensitive and selective two-dimensional high-performance liquid chromatographic system combining a reversed-phase column and an enantioselective column. The circadian rhythm was not changed under fasting conditions. In the mice lacking d-amino acid oxidase activity (ddY/DAO^- mice), clear day–night changes were still observed, suggesting that the factors controlling the d-Ala rhythm were not their food and DAO activity. On the other hand, in the germ-free mice, quite low amounts of d-Ala were detected compared with those in the control mice, indicating that the main origin of d-Ala in the mice is intestinal bacteria. Because the d-Ala amounts in the digesta containing intestinal bacteria did not show the day–night changes, the controlling factor of the circadian changes of the d-Ala amount was suggested to be the intestinal absorption.     

The effect of compositions and combinations of the reactants upon the copolycondensation of isophthalic acid/terephthalic acid with a combination of hydroquinones and bisphenols by tosyl chloride/dimethylformamide/pyridine

Copolycondensation of isophthalic acid (IPA)/terephthalic acid (TPA) with various combinations of 2,2‐bis(4‐hydroxyphenyl)propane (BPA) and hydroquinones (HQs) or bisphenols (BPs) was conducted to study the effects of the compositions of IPA/TPA and of BPA/HQs or BPA/BPs upon the reaction. Different from homopolycondensation of each of diol components examined where most of the reaction was facilitated by lower contents of IPA at about 70 mol %, the copolycondensation was influenced by a combination of diol components. With chlorohydroquinone (ClHQ) or bis(4‐hydroxyphenyl)sulfone (BPS) having a polar chlorine or sulfonyl substituent, the reaction proceeded most satisfactorily at IPA/TPA = 30/70, whereas it was IPA/TPA = 50/50 for the reaction with nonpolar methyl substituted methylhydroquinone (MeHQ). The reaction with 2,2‐bis(3,5‐dichloro‐4‐hydroxyphenyl)propane (TC‐BPA), despite having polar chlorine substituents in TC‐BPA, was not affected by IPA/TPA compositions. Alternatively, from the viewpoint of the compositions of diol components, the reactions containing 30–50 mol % of HQs or BPS yielded better results except for the reaction of IPA/TPA = 70/30, in which higher contents of MeHQ was more favorable. On the basis of sequence distributions of diol components in the resultant copolymers determined by NMR, compositions of IPA/TPA or diol components and combinations of the diols producing random copolymers yielded better results in copolycondensation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1100–1106, 2004