An electron diffraction determination of the molecular structures of silyl- and germyl-manganese pentacarbonyl in the gas phase

The molecular structures of the title compounds have been determined by gas phase electron diffraction methods. The SiMn and GeMn bond lengths are 240.7 ? 0.5 and 248.7 ? 0.2 pm respectively and the CMnC angles in the silyl and germyl cases are 94.5 ± 2° and 97 ± 2° respectively. Comparisons are made with the reported structure of CH₃Mn(CO)₅ and He^I photoelectron spectra of these compounds in an attempt to determine the extent of d → d π-bonding in the SiMn or GeMn bonds.     

Platination of [3-X-7,8-Ph2-7,8-nido-C2B9H8] (X=Et, F): Synthesis and characterisation of slipped and 1,2→1,7 isomerised products

The reaction of the labelled carborane ligand [3-Et-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ with a source of {Pt(PMe₂Ph)₂}²⁺ affords non-isomerised 1,2-Ph₂-3,3-(PMe₂Ph)₂-6-Et-3,1,2-closo-PtC₂B₉H₈ (1). The analogous reaction between [3-F-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ and {Pt(PMe₂Ph)₂}²⁺ yields 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-F-2,1,8-closo-PtC₂B₉H₈ (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-Et-2,1,8-closo-PtC₂B₉H₈ (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB₂ face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques.     

次级键与晶体中锑(III)螯合物配位多面体研究

考虑立体活性孤对电子附近次级键配位原子的贡献, 对文献报道的三十个氨基多羧酸锑(III)螯合物的晶体结构中配位多面体描述进行了全面的修正. 配位多面体的几何构型指定采用了单位球内截多面体的两面角判据及其相关的ANVPDA程序. 所有配位多面体几何构型的修正均得到了键价计算的有力支持.     

Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2'-dithiolates, and related ligands

Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The pro-ligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp(2)TiS(2)Ar complexes (Ar = naphthalene) have been shown by temperature-dependent (1)H NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS(2)C(3) rings undergoing inversion on the NMR time scale while the similar Cp(2)TiS(2)Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO(2) groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.     

Polymerization by alkaline earth metal compounds—I. Studies on the polymerization of methylmethacrylate by triphenylmethyl metal derivatives and related compounds of calcium,strontium and barium

A series of related organo-alkaline earth metal compounds of formula (Ph₃C)MX(THF)_η, (M = Ca, Sr, Ba; X = Cl: M = Ca, Sr; X = Br: M = Ba; X = CPh₃), has been isolated and characterized using analytical and spectroscopic techniques. The polymerization of methylmethacrylate (MMA) has been studied using these organometallic compounds as initiators. Investigations of the tacticity variations of polymethylmethacrylate (PMMA) produced in 1,2-dimethoxyethane or tetrahydrofuran (THF) at 210 K have shown that the syndiotacticity is higher in the former solvent, decreases with the following changes in initiator composition: Ca > Sr ? Ba; Cl > Br; in THF, it is dependent on the monomer concentration. The molecular weight distributions of the PMMA samples are broad and have distinct bi- or poly-modal features. The polymerization process appears to be anionic in nature but the evidence suggests that more than one type of propagation occurs and mechanistic aspects are discussed. Polymerization of bulk MMA by these same initiators is also reported. The initiators RMX(THF)_n (M = Sr, R = Me, n = 3 or R = Et, n = 2) and (C₃H₅)SrBr(THF)₂ are shown to be inefficient for polymerization of MMA. The glass transition temperatures of a range of PMMA samples of differing tacticity are presented and discussed.     

A stratospheric chemical reaction controlling climatic change

It has been established from geological studies that change in the atmospheric content of carbon dioxide gas commenced about one hundred million years ago. The likely origin of this change is advanced as being the onset of the Brewer circulation caused by the rise in terrain induced by tectonic plate movement. It is demonstrated that tectonic plate movement can be affected by impacts from external bodies which penetrate the crust of the Earth. The consequences of the change in atmospheric concentration of carbon dioxide are proposed as first, extinctions and reductions in animal numbers, including primates, as a result of changes in body chemistry of these animals and second, a change in the rate of weathering of rocks giving rise to changes in the availability of chemicals such as calcium and potassium which are essential for plant and animal life. This latter change contributing to the extinctions and reductions in animal numbers. It is shown that the change in weathering can account for the rise to dominance of angiosperm plants. It is concluded that there were several simultaneous evolutionary environments on Earth which were a function of altitude which gave rise to a vertical variation in atmospheric content of carbon dioxide. This variation disappeared with rise of terrain and the onset of the Brewer circulation. Such changes are advanced and being much more important than any changes in temperature caused by greenhouse effects since the disappearance of atmospheric variations in carbon dioxide allowed animal migration. It is demonstrated that the conditions of extinction could be reintroduced by human activities.     

Chloroplast Biogenesis 77: Two Novel Monovinyl and Divinyl Light-Dark Greening Groups of Plants and Their Relationship to the Chlorophyll a Biosynthetic Heterogeneity of Green Plants

Abstract— On the basis of the steady-state accumulation of divinyl (DV) or monovinyl (MV) protochlorophyllide (Pchlide) a in darkness (D) or in the light (L), green plants have been classified into three different greening groups namely dark divinyl-light divinyl (DDV-LDV), dark monovinyl-light divinyl (DMV-LDV) and dark monovinyl-light monovinyl (DMV-LMV) (Ionannides et al., Biochem. Syst. Ecol. 22, 211-220,1994). Interruption of the L phase of the photoperiod by a brief period of darkness (LD condition) revealed a predominance of different chlorophyll (Chl) a biosynthetic routes, depending upon the greening group affiliation of the plant species. For example, in DMV-LDV and DMV-LMV plants, the predominant Chl a biosynthetic routes under the LD condition appear to be the MV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Pchlide a. On the basis of DV and MV Pchlide a accumulation rates after re-darkening, this greening group is designated as a light-dark MV (LDMV) subgroup. In DDV-LDV plants, the predominant LD Chi a biosynthetic routes appear to be the DV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Chlide a. This greening group is designated as a light-dark DV (LDDV) subgroup. It is proposed that upon inhibiting the conversion of Pchlide a to Chi a by interruption of the L phase of the photoperiod by a brief period of D, the rates of DV and MV Pchlide a regeneration may reflect the carryover rates of DV and MV Pchlide a biosynthesis in L instead of reflecting a differential use of DV and MV carboxylic biosynthetic rates in D. It is also shown that in LDMV plants, MV Chlide a and MV Chi a are formed without the participation of [4-vinyl] Chlide a reductase. On the basis of recently published evidence, it is also argued that Pchlide oxidoreductase-A (POR-A) may be active in LDDV plants, while POR-B may predominate in LDMV plant species. The evolutionary significance of the LDDV and LDMV greening subgroups is discussed.     

Ramsey partitions of integers and pair divisions

Ifk ₁ andk ₂ are positive integers, the partitionP = (₁,₂,..., _n ) ofk ₁+k ₂ is said to be a Ramsey partition for the pairk ₁,k ₂ if for any sublistL ofP, either there is a sublist ofL which sums tok ₁ or a sublist ofP –L which sums tok ₂. Properties of Ramsey partitions are discussed. In particular it is shown that there is a unique Ramsey partition fork ₁,k ₂ having the smallest numbern of terms, and in this casen is one more than the sum of the quotients in the Euclidean algorithm fork ₁ andk ₂.An application of Ramsey partitions to the following fair division problem is also discussed: Suppose two persons are to divide a cake fairly in the ratiok ₁k ₂. This can be done trivially usingk ₁+k ₂-1 cuts. However, every Ramsey partition ofk ₁+k ₂ also yields a fair division algorithm. This method yields fewer cuts except whenk ₁=1 andk ₂=1, 2 or 4.     

Fluorenyl-containing sulfonated poly(aryl ether ether ketone ketone)s (SPFEEKK) for fuel cell applications

A series of fluorenyl-containing sulfonated poly(aryl ether ether ketone ketone)s (SPFEEKK) were synthesized via aromatic nucleophilic substitution polymerization. The sulfonation content (SC) was controlled by the feed ratios of sulfonated and nonsulfonated monomers. Flexible and strong membranes in the sulfonic acid form were obtained from cast membranes in the sodium salt forms by treatment with acid. The thermal properties, water uptake, swelling ratio, water state, oxidative stability, proton conductivity and methanol permeability were investigated. All the polymers had proton conductivities greater than 1 × 10⁻² S/cm at room temperature, and the conductivity values of m-SPFEEKK-80 and p-SPFEEKK-80 were up to 1.86 × 10⁻¹ and 1.78 × 10⁻¹ S/cm at 100 °C. This series of polymers also possessed good dimensional stability in water and low methanol crossover.