Unsaturated σ-hydrocarbyl transition-metal complexes. Part 4. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)-(phenylethynyl)platinum(II) and comments on the relative trans influence of various carbon ligands

The molecular structure of trans-[PtCl(CCPh)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21, with a= 12.359(3), b= 13.015(3), c= 9.031(2)Å, β= 101.65(2)°, and Z= 2. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.046 for 1 877 diffractometric intensity data. The crystals contain discrete molecules in which the platinum coordination is square planar. The phenylethynyl group is non-linear, with a Pt–CC angle of 163(2)°. Selected bond lengths are Pt–Cl 2.407(5) and Pt–C 1.98(2)Å. The structural trans influences of CCPh, CHCH2, and CH2SiMe3 ligands in platinum(II) complexes are compared; there is only a small dependence on hybridization at the ligating carbon atom.

Syntheses and crystal structures of [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], two novel heteroleptic tin(II) compounds derived from [Sn-{2-[(Me3Si)2C]C5H4N}Cl], and for [{Sn(C6H2Pri3-2,4,6)2}3] 3, a structural redetermination

Two novel, monomeric heteroleptic tin(II) derivatives, [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], have been prepared, characterised by multinuclear NMR spectroscopies and their molecular structures determined by single crystal X-ray diffraction. Both compounds were prepared from the corresponding heteroleptic tin(II) chloro-analogue, [Sn{2-[(Me3Si)2C]C5H4N}Cl], and thus demonstrate the utility of this compound as a precursor to further examples of heteroleptic tin(II) derivatives: such compounds are often unstable with respect to ligand redistribution. In each case, the central tin(II) is three-co-ordinate. Crystals of trimeric [{Sn(C6H2Pri3-2,4,6)2}3] 3 were found to undergo a solid state phase transition, which may be ascribed to ordering of the ligand isopropyl groups. At 220 K the unit cell is orthorhombic, space group Pna21, compared with monoclinic, space group P21/c, for the same crystals at 298 K, in which there is an effective tripling of the now b (originally c) axis. This result illustrates the extreme crowding generated by this bulky aryl ligand.

Binuclear and polymeric manganese(II) salicylate complexes: synthesis, crystal structure and catalytic activity of [Mn2(Hsal)4(H2O)4] and [{Mn2(sal)2(Hsal)(H2O)-(H3O)(py)4•2py}n](H2sal = salicylic acid, py = pyridine)

The two air-stable manganese(II) salicylate complexes [Mn2(Hsal)4(H2O)4]1 and polymeric [{Mn2(sal)2(Hsal)(H2O)(H3O)(py)4·2py}n]2(H2sal = salicylic acid and py = pyridine) have been synthesised easily, and their crystal structures determined. Both contain unsymmetrically bridging salicylate ligands. In the presence of added pyridine 1 and 2 vigorously catalyse the disproportionation of H2O2.

Reaction of 4-phenylbut-3-en-2-one with cyanoacetamide in 2:1 ratio

The reaction of 4-phenylbut-3-en-2-one with cyanoacetamide is not confined to a 1 : 1 reaction [which results in formation of 3-cyano-6-methyl-4-phenylpyridin-2(1H)-one]. The reaction of 2 mole equivalents of 4-phenylbut-3-en-2-one with one of cyanoacetamide also takes place, the products being 1-cyano-6-hydroxy-6-methyl-4-methylene-8,9-diphenyl-3-azabicyclo[3.3.1]nonan-2-one and 3-cyano-6-methyl-3-(3-oxo-1-phenylbutyl)-4-phenyl-3,4-dihydropyridin-2(1H)-one. The latter compound cyclises in acid medium to form 6-acetyl-4-cyano-1-methyl-5,8-diphenyl-2-azabicyclo[2.2.2]octan-3-one. X-Ray crystal structures of the 3-azabicyclo[3.3.1]nonan-2-one and the 3-azabicyclo[2.2.2]octan-2-one derivatives are described.

Platonic allusion in Plutarch's Alcibiades 4-7

Plutarch deals with Socrates' relationship with Alcibiades in chs. 4-7 of his Life. He draws heavily here on two Platonic works, the First Alcibiades and the Symposium, but engagement with the Platonic texts is denser and more profound in Alcibiades than a study of just those two texts would suggest. In fact, this part of the Alcibiades contains allusions to several other Platonic texts in which Alcibiades does not occur as a character and in which his name is not mentioned: Republic Books 6 and 8, Charmides, Phaedrus, Apology, and Lysis. These texts function as ‘intertexts’ against which the Alcibiades is to be read.

The cloud chamber and CTR Wilson’s legacy to atmospheric science

2011 is the centenary year of the short paper (Wilson,1911) first describing the cloud chamber, the device for visualising high-energy charged particles which earned the Scottish physicist Charles Thomas Rees (‘CTR’) Wilson the 1927 Nobel Prize for physics. His many achievements in atmospheric science, some of which have current relevance, are briefly reviewed here. CTR Wilson’s lifetime of scientific research work was principally in atmospheric electricity at the Cavendish Laboratory, Cambridge; he was Reader in Electrical Meteorology from 1918 and Jacksonian Professor from 1925 to 1935. However, he is immortalised in physics for his invention of the cloud chamber, because of its great significance as an early visualisation tool for particles such as cosmic rays1 (Galison, 1997). Sir Lawrence Bragg summarised its importance:

The vertical cloud structure of the West African monsoon: a 4 year climatology using CloudSat and CALIPSO

The West African summer monsoon (WAM) is an important driver of the global climate and locally provides most of the annual rainfall. A solid climatological knowledge of the complex vertical cloud structure is invaluable to forecasters and modelers to improve the understanding of the WAM. In this paper, 4 years of data from the CloudSat profiling radar and CALIPSO are used to create a composite zonal mean vertical cloud and precipitation structure for the WAM. For the first time, the near-coincident vertical radar and lidar profiles allow for the identification of individual cloud types from optically thin cirrus and shallow cumulus to congestus and deep convection. A clear diurnal signal in zonal mean cloud structure is observed for the WAM, with deep convective activity enhanced at night producing extensive anvil and cirrus, while daytime observations show more shallow cloud and congestus. A layer of altocumulus is frequently observed over the Sahara at night and day, extending southward to the coastline, and the majority of this cloud is shown to contain supercooled liquid in the top. The occurrence of deep convective systems and congestus in relation to the position of the African easterly jet is studied, but only the daytime cumulonimbus distribution indicates some influence of the jet position.

Dealing with complexity: an autopoietic view of the People's Planning Campaign, Kerala

Complexity is integral to planning today. Everyone and everything seem to be interconnected, causality appears ambiguous, unintended consequences are ubiquitous, and information overload is a constant challenge. The nature of complexity, the consequences of it for society, and the ways in which one might confront it, understand it and deal with it in order to allow for the possibility of planning, are issues increasingly demanding analytical attention. One theoretical framework that can potentially assist planners in this regard is Luhmann's theory of autopoiesis. This article uses insights from Luhmann's ideas to understand the nature of complexity and its reduction, thereby redefining issues in planning, and explores the ways in which management of these issues might be observed in actual planning practice via a reinterpreted case study of the People's Planning Campaign in Kerala, India. Overall, this reinterpretation leads to a different understanding of the scope of planning and planning practice, telling a story about complexity and systemic response. It allows the reinterpretation of otherwise familiar phenomena, both highlighting the empirical relevance of the theory and providing new and original insight into particular dynamics of the case study. This not only provides a greater understanding of the dynamics of complexity, but also produces advice to help planners implement structures and processes that can cope with complexity in practice.

Three dimensional picture of the local structure of 1,4-Polybutadiene from a complete atomistic model and neutron scattering data

An efficient method of combining neutron diffraction data over an extended Q range with detailed atomistic models is presented. A quantitative and qualitative mapping of the organization of the chain conformation in both glass and liquid phase has been performed. The proposed structural refinement method is based on the exploitation of the intrachain features of the diffraction pattern by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Models are built stochastically by assignment of these internal coordinates from probability distributions with limited variable parameters. Variation of these parameters is used in the construction of models that minimize the differences between the observed and calculated structure factors. A series of neutron scattering data of 1,4-polybutadiene at the region 20320 K is presented. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54 and 1.35 Å respectively. Valence angles of the backbone were found to be at 112 and 122.8 for the CCC and CC=C respectively. Three torsion angles corresponding to the double bond and the adjacent R and β bonds were found to occupy cis and trans, s(, trans and g( and trans states, respectively. We compare our results with theoretical predictions, computer simulations, RIS models, and previously reported experimental results.

The 'algebra as object' analogy: a view from school

Treating algebraic symbols as objects (eg. “‘a’ means ‘apple’”) is a means of introducing elementary simplification of algebra, but causes problems further on. This current school-based research included an examination of texts still in use in the mathematics department, and interviews with mathematics teachers, year 7 pupils and then year 10 pupils asking them how they would explain, “3a + 2a = 5a” to year 7 pupils. Results included the notion that the ‘algebra as object’ analogy can be found in textbooks in current usage, including those recently published. Teachers knew that they were not ‘supposed’ to use the analogy but not always clear why, nevertheless stating methods of teaching consistent with an‘algebra as object’ approach. Year 7 pupils did not explicitly refer to ‘algebra as object’, although some of their responses could be so interpreted. In the main, year 10 pupils used ‘algebra as object’ to explain simplification of algebra, with some complicated attempts to get round the limitations. Further research would look to establish whether the appearance of ‘algebra as object’ in pupils’ thinking between year 7 and 10 is consistent and, if so, where it arises. Implications also are for on-going teacher training with alternatives to introducing such simplification.