配位副反应系数的实验测定

提出了配位副反应系数的实验测定方法．本方法手续与计算简便，试用于钢（铀）－偶氮胂Ⅰ体系，获得了令人满意的结果．     

Complexation of neptunium(V) by salicylate,phthalate and citrate ligands in a pH 7.5 phosphate buffered system

Conditional stability constants, enthalpies and entropies of complexation at pH 7.5 and ionic strength 0.1 have been determined for neptunium(V) complexes of phosphate, salicylate, phthalate and citrate. Phosphate forms a complex with log β = 2.36 ± 0.42 at 25°C, ΔH°_c = ? 69.9 kJ/mole and ΔS°_c = ? 188 J/mole-K. At pH 7.5 salicylate does not form a complex with neptunium(V) due to the low charge density of the NpO₂⁺ ion and incomplete ionization of the salicylate ion. Phthalate forms a complex with log β = 3.43 ± 0.33 at 25°C, ΔH°_c = 33.5 kJ/mole and ΔS°_c = 182 J/mole-K. Citrate forms a complex with log β = 4.84 ± 0.72 at 25°C, ΔH°_c = 14.0 kJ/mole and ΔS°_c = 140 J/mole-K. In all cases, only 1:1 complexes were identified.     

The number of faces of balanced Cohen-Macaulay complexes and a generalized Macaulay theorem

A Cohen-Macaulay complex is said to be balanced of typea=(a ₁,a ₂, ...,a _s ) if its vertices can be colored usings colors so that every maximal face gets exactlya _i vertices of thei:th color. Forb=(b ₁,b ₂, ...,b _s ), 0≦b≦a, letf _b denote the number of faces havingb _i vertices of thei:th color. Our main result gives a characterization of thef-vectorsf=(f _b )_0≦b≦a′ or equivalently theh-vectors, which can arise in this way from balanced Cohen-Macaulay complexes. As part of the proof we establish a generalization of Macaulay’s compression theorem to colored multicomplexes. Finally, a combinatorial shifting technique for multicomplexes is used to give a new simple proof of the original Macaulay theorem and another closely related result. First and third authors partially supported by the National Science Foundation.     

Generalised Ramsey numbers for small graphs

The generalised Ramsey number R(G₁, G₂,..., G_k) is defined as the smallest integer n such that, if the edges of K_n, the complete graph on n vertices, are coloured using k colours C₁, C₂,..., C_k, then for some i(1≤i≤k) there is a subgraph G_i of K_n with all of its edges colour C_i. When G₁=G₂=...,G_k=G, we use the more compact notation R_k(G).The generalised Ramsey numbers R_k(G) are investigated for all graphs G having at most four vertices (and no isolates). This extends the work of Chvátal and Harary, who made this investigation in the case k=2.     

Observation of helicon-excited electron paramagnetic resonance in a high-mobility semiconductor

Helicon waves can be exploited in EPR studies of localized magnetic moments in high-conductivity semiconductors when the free carriers have small effective mass and high mobility. In an electron plasma helicons have precisely the polarization required to elicit EPR, and the plasma background actually enhances the resonance intensity. Microwave transmission experiments on Hg_1-xMn_xTe, a narrow-gap semiconductor with localized Mn⁺⁺ magnetic moments, are described to illustrate this effect.     

Sulfur heterocycles. II. The hydroxyoxathiolane to acyloin rearrangement

Thermal control of demasking conditions may be used to convert hydroxyoxathiolanes into either α-hydroxyaldehydes or the corresponding ring-expanded acyloins.     

Reactions of Grignard reagents from 1-halogenoallenes. Allenes—XXXIII

Grignard reagents have been prepared from 1-bromo-3,3-dialkylallenes in ether or tetrahydrofuran. The allenic acids, 4,4-dialkylbuta-2,3-dienoic acids together with 4,4-dialkylbut-2-ynoic acids are formed with carbon dioxide to the exclusion of acids with a terminal acetylene group. Two coupled products, 3,4-diethyl-3,4-dimethylhexa-1,5-diyne and 3-ethyl-3,6-dimethylocta-4,5-dien-1-yne, which are formed as byproducts in reactions of 3-methylpenta-1,2-dienyl magnesium bromide with electrophiles (CO₂, H₂O, Me₂CO), are obtained in high yield by passing oxygen through the solution of the Grignard reagent.     

Geometry optimised ab inttio calculations on 1,5- and 1,2-dicarba-closo-pentaborane (5)

Geometry optimised ab initio LCAO- MO-SCF calculations for the isomeric carboranes 1,5- and 1,2-dicarba-closo-pentaborane (5) are reported. The optimised geometry of the 1,5-isomer agrees with the experimental geometry and for this isomer greater thermo-dynamic stability is predicted. The framework bonding is due mainly to interactions between the apical atoms and those in the equatorial plane, while within this equatorial plane there is very weak bonding.     

The crystal and molecular structure of the dimethylplatinum(II) complex of 1,1,1-tris(diphenylphosphinomethyl)ethane

A new crystal X-ray study, as well as proton and phosphorus-31 NMR studies, show that the structure of Pt(CH₃)₂(tripod) [tripod = 1,1,1-tris(diphenylphosphinomethyl)ethane] consists of a four-coordinate, nearly planar platinum with the triphosphine functioning as a bidentate ligand.