The structure of (dichloro) (DI-μ-acetato)(bis-triphenyl phosphine) dimolybdenum(II)

The title compound was obtained in crystalline form suitable for X-ray structure determination. It forms crystals in the monoclinic space group P2₁/c with two centrosymmetric molecules in a unit cell of dimensions, a = 10.888(1) Å, b = 10.182(2) Å, c = 17.929(4) Å, β = 104.33(1)°. The central Mo₂Cl₂(O₂C)₂P₂ core has effectively C_2h-symmetry with the following principal dimensions: MoMo = 2.091(1) Å, MoCl = 2.405 Å, MoP = 2.566(2) Å, MoO(av.) = 2.103[4] Å, MoMoP = 104.38(7)°, and MoMoCl = 116.23(8)°.     

Cation transport at 25°c from binary Tl+Mn+ and K+Mn+ nitrate mixtures in a H2OCHCl3H2O liquid membrane system containing a series of macrocyclic polyether carriers

Carrier-mediated cation fluxes were determined using a H₂OCHC1₃H₂O liquid merebrane system for TlNO₃ and for binary mixtures of either TlNO₃ or KNO₃ with alkali metal ions, alkaline earth metal ions, and Pb²⁺ (in the case of TlNO₃). Both macrocyclic polyether and cryptand ligands were used as carriers. In Tl⁺Mⁿ⁺ mixtures, selective transport of Tl⁺ was found over all cations studied, except in the cases of Ag⁺ by 2.2 and of Pb²⁺ by 18C6, DC18C6, ClDKP18C6, and 2.2. Generally, K⁺ was transported selectively from K⁺Mⁿ⁺ mixtures, except in the cases of K⁺Tl⁺ mixtures in which Tl⁺ was transported selectively in all cases. A model relating cation flux to log K(CH₃OH) for Mⁿ⁺—macrocycle interaction and to ion-partitioning between the organic and aqueous phases was successful in rationalizing selective cation transport in most of the systems studied.     

Kinetics of the reaction of Di-μ-acetatodi-μ-oxalatodiaquodiruthenium(II,III) anion with N-(2-hydroxyethyl)-ethylenediaminetriacetatoaquotitanium(III)

Reduction of [Ru₂(CH₃COO)₂(C₂O₄)₂(H₂O)₂]^? by N-(2-hydroxyethyl)-ethylenediaminetriacetatoaquotitanium(III) [Ti(HEDTA)] involves several distinct stages. The first stage has a half-time of less than 1 ms, and is interpreted as a substitution reaction leading to a multinuclear intermediate. The second stage has a second-order rate constant of 5 x 10₃M^?1s^?1 [25°C, μ = 0.1 m (LiCF₃SO₃)]. The rate-limiting process for the second stage is electron transfer within the assembled multinuclear complex. Subsequent slower stages correspond to breakup of the multinuclear Ru(II)₂-Ti(IV) complex formed by electron transfer. The overall rate of reduction of this oxidant by Ti(HEDTA) is less than the corresponding rate for the reaction in which Ti³⁺ acts as reductant, mainly because the stability of the binuclear complex is reduced by the presence of the aminoacid ligand. The data are consistent with the conclusion that the ligand increases the rate of intramolecular ET, probably by reducing geometric change associated with oxidation of Ti(III) to Ti(IV).     

A crucial demonstration of strong collisional behavior of vibrational energy for gas-surface collisions

Application of the variable encounter method (VEM) has been made to the thermal cyclobutene decomposition system. Vibrational energy transfer in the cyclobutene-seasoned quartz surface system has been studied. The occurrence of strong collisions is demonstrated in crucial manner at temperatures below 400 K.     

Interpretation of the vibrational spectra of methylglyoxal and biacetyl in their first singlet excited electronic states

Laser-induced fluorescence spectra for the first allowed electronic transition (22125 cm^?1) of methylglyoxal (CH₃COCHO) and its perdeutero analog (CD₃COCDO) in a supersonic nozzle beam are quantitatively represented assuming that the potential function governing the CH₃(CD₃) rotation is changed during the transition. In the excited state the potential function is ternary (V₁ = 95 (1 + cos 3θ)cm^?1) as in the fundamental state (V₀ = 134.5 (1 - cos 3θ)cm^?1), but the minima are shifted by an angle of π/3. The spectrum of biacetyl (CH₃COCH₃CO) can be reproduced assuming two uncoupled methyl groups undergoing similar conformational changes during the electronic transition (the estimated potential function is V₁ = 117.5 (1 + cos 3θ) cm^?1 for each methyl group), in perfect agreement with the most recent assignment of the 0-0 transition. These results are consistent with ab initio calculations for the fundamental and first excited singlet states.     

关于S^n＋p和CP^n＋p中的极小子流形

本文改进了分别由Ｓ．Ｔ．Ｙａｕ，Ａ．Ｒｏｓ及沈一兵给出的关于单位球面Ｓｎ＋ｐ的极小流形和复射影空间ＣＰ＾ｎ＋ｐ的Ｋａｅｈｌｅｒ子流形及全实极小子流形的截面曲率的Ｐｉｎｃｈｉｎｇ常数。     

Diorganotin(IV) bis(O,O-alkylenedithiophosphates)

O,O-Alkylenedithiophosphates of diorganotin(IV) of the type R₂Sn[SP(S)O₂G]₂ (R = Me, Et, n-Bu, Ph; G = CH₂CMe₂CH₂, CMe₂CMe₂, CMe₂CH₂CHMe) have been synthesized by the reactions of diorganotin(IV) dichlorides with ammonium O,O-alkylenedithiophosphates or that of diorganotin(IV) oxides with O,O-alkylenedithiophosphoric acids in 1:2 molar ratio in benzene. These new complexes are white solids which are soluble in common organic solvents and are monomeric in refluxing benzene; and they have been characterized by elemental analysis and by different spectroscopic (IR, ¹H, ¹³C, ³¹P and ¹¹⁹Sn NMR) studies, on the basis of which a six coordinated octahedral structure has been suggested in solution.