Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

Solvothermal synthesis of novel antimony sulphides containing [Sb4S7](2-) units

Two new antimony sulphides have been prepared solvothermally and characterised by single-crystal X-ray diffraction. [Co(en)(3)][Sb4S7] (1) was prepared at 140 degreesC from COS, Sb2S3 and S in the presence of ethylenediamine, whilst heating a mixture of Sb2S3, Co and S in tris(2aminoethyl)amine, N(CH2CH2NH2)(3), at 180 degreesC fegults in the formation of [C6H20N4][Sb4S7] (2). Both materials contain [Sb4S7](2-) chains formed from linkage of cyclic Sb3S63- units by SbS33- pyramids. In (1), the [Sb4S7] chains are linked by secondary Sb-S interactions to form sheets, between which the. charge balancing [Co(en)(3)](2+) cations reside. The structure of (2) involves interconnection of pairs of [Sb4S7](2-) chains through Sb2S2 rings to form isolated [Sb4S7](2-) double chains which are interleaved by protonated template molecules. (C) 2004 Elsevier B.V. All rights resereved.

Photochromic dithienylethene derivatives containing Ru(II) or Os(II) metal units. Sensitized photocyclization from a triplet state

Efficient photocyclization from a low-lying triplet state is reported for a photochromic dithienylperfluorocyclopentene with Ru(bpy)(3) units attached via a phenylene linker to the thiophene rings. The ring-closure reaction in the nanosecond domain is sensitized by the metal complexes. Upon photoexcitation into the lowest Ru-to-bpy (MLCT)-M-1 state followed by intersystem crossing to emitting (MLCT)-M-3 states, photoreactive (IL)-I-3 states are populated by an efficient energy-transfer process. The involvement of these (IL)-I-3 states explains the quantum yield of the photocyclization, which is independent of the excitation wavelength but decreases strongly in the presence of dioxygen. This behavior differs substantially from the photocyclization of the nonemissive dithienylperfluorocyclopentene free ligand, which occurs from the lowest (IL)-I-1 state on a picosecond time scale and is insensitive to oxygen quenching. Cyclic voltammetric studies have also been performed to gain further insight into the energetics of the system. The very high photocyclization quantum yields, far above 0.5 in both cases, are ascribed to the strong steric repulsion between the bulky substituents on the dithienylperfluorocyclopentene bridge bearing the chelating bipyridine sites or the Ru(bpy)(3) moieties, forcing the system to adopt nearly exclusively the reactive antiparallel conformation. In contrast, replacement of both Ru(II) centers by Os(II) completely prevents the photocyclization reaction upon light excitation into the low-lying Os-to-bpy (MLCT)-M-1 state. The photoreaction can only be triggered by optical population of the higher lying (IL)-I-1 excited state of the central photochromic unit, but its yield is low due to efficient energy transfer to the luminescent lowest (MLCT)-M-3 state.

An unusual axial–axial combination of alternating cyclic rings in the chair conformations of hexameric water and chlorine-water clusters

An alternating hexameric water (H2O)(6) cluster and a chlorine-water cluster [Cl-2(H2O)(4)](2-) in the chair forms combine axially to each other to form a 1D chain [{Cl-2(H2O)(6)}(2-)](n) in complex [FeL2]Cl center dot(H2O)(3) (L=2-[(2-methylaminoethylimino)-methyl]-phenol)]. The water molecules display extensive H-bonding interactions with monomeric iron-organic units to form a hydrogen-bonded 2D supramolecular assembly.

Quantifying sediment transport processes in periglacial mountain environments at a catchment scale using geomorphic process units

The research record on the quantification of sediment transport processes in periglacial mountain environments in Scandimvia dates back to the 1950s. A wide range of measurements is. available, especially from the Karkevagge region of northern Sweden. Within this paper satellite image analysis and tools provided by geographic information systems (GIS) are exploited in order to extend and improve this research and to complement geophysical methods. The processes of interest include mass movements such as solifluction, slope wash, dirty avalanches and rock-and boulder falls. Geomorphic process units have been derived in order to allow quantification via GIS techniques at a catchment scale. Mass movement rates based on existing Field measurements are employed in the budget calculation. In the Karkevagge catch ment. 80% of the area can be identified either as a source area for sediments or as a zone where sediments are deposited. The overall budget for the slopes beneath the rockwalls in the Karkevagge is approximately 680 t a(-1) whilst about 150 : a-1 are transported into the fluvial System.

Mapping the spatial distribution of geomorphological processes in the Okstindan area of northern Norway, using Geomorphic Process Units as derived from remote sensing and ground survey

The delineation of Geomorphic Process Units (GPUs) aims to quantify past, current and future geomorphological processes and the sediment flux associated with them. Five GPUs have been identified for the Okstindan area of northern Norway and these were derived from the combination of Landsat satellite imagery (TM and ETM+) with stereo aerial photographs (used to construct a Digital Elevation Model) and ground survey. The Okstindan study area is sub-arctic and mountainous and is dominated by glacial and periglacial processes. The GPUs exclude the glacial system (some 37% of the study area) and hence they are focussed upon periglacial and colluvial processes. The identified GPUs are: 1. solifluction and rill erosion; 2. talus creep, slope wash and rill erosion; 3. accumulation of debris by rock and boulder fall; 4. rockwalls; and 5. stable ground with dissolved transport. The GPUs have been applied to a ‘test site’ within the study area in order to illustrate their potential for mapping the spatial distribution of geomorphological processes. The test site within the study area is a catchment which is representative of the range of geomorphological processes identified.

Enantioselective Intramolecular Michael Addition of Nitronates onto Conjugated Esters: Access to Cyclic γ-Amino Acids with up to Three Stereocenters

A highly stereoselective synthesis of conformationally constrained cyclic γ-amino acids has been devised. The key step involves an intramolecular cyclization of a nitronate onto a conjugated ester, promoted by a bifunctional thiourea catalyst. This methodology has been successfully applied to generate a variety of γ-amino acids, including some containing three contiguous stereocenters, with very high diastereoselectivity and excellent enantioselectivity. It is postulated that an interaction that is key to the success of the process is the simultaneous coordination of the thiourea functionality to both the conjugated ester and the nitronate. Finally, the synthetic utility of these compounds is demonstrated in the synthesis of two dipeptides derived from the C- and N-termini.

Quantities, units and symbols in physical chemistry, 3rd edition

The first IUPAC Manual of Symbols and Terminology for Physicochemical Quantities and Units (the Green Book) of which this is the direct successor, was published in 1969, with the object of 'securing clarity and precision, and wider agreement in the use of symbols, by chemists in different countries, among physicists, chemists and engineers, and by editors of scientific journals'. Subsequent revisions have taken account of many developments in the field, culminating in the major extension and revision represented by the 1988 edition under the simplified title Quantities, Units and Symbols in Physical Chemistry. This 2007, third edition, is a further revision of the material which reflects the experience of the contributors with the previous editions. The book has been systematically brought up to date and new sections have been added. It strives to improve the exchange of scientific information among the readers in different disciplines and across different nations. In a rapidly expanding volume of scientific literature where each discipline has a tendency to retreat into its own jargon this book attempts to provide a readable compilation of widely used terms and symbols from many sources together with brief understandable definitions. This is the definitive guide for scientists and organizations working across a multitude of disciplines requiring internationally approved nomenclature.

A concise summary of the International System of Units, the SI

The Bureau International des Poids et Mesures, the BIPM, was established by Article 1 of the Convention du Mètre, on 20 May 1875, and is charged with providing the basis for a single, coherent system of measurements to be used throughout the world. The decimal metric system, dating from the time of the French Revolution, was based on the metre and the kilogram. Under the terms of the 1875 Convention, new international prototypes of the metre and kilogram were made and formally adopted by the first Conférence Générale des Poids et Mesures (CGPM) in 1889. Over time this system developed, so that it now includes seven base units. In 1960 it was decided at the 11th CGPM that it should be called the Système International d’Unités, the SI (in English: the International System of Units). The SI is not static but evolves to match the world’s increasingly demanding requirements for measurements at all levels of precision and in all areas of science, technology, and human endeavour. This document is a summary of the SI Brochure, a publication of the BIPM which is a statement of the current status of the SI. The seven base units of the SI, listed in Table 1, provide the reference used to define all the measurement units of the International System. As science advances, and methods of measurement are refined, their definitions have to be revised. The more accurate the measurements, the greater the care required in the realization of the units of measurement.

On logarithmic ratio quantities and their units

The use of special units for logarithmic ratio quantities is reviewed. The neper is used with a natural logarithm (logarithm to the base e) to express the logarithm of the amplitude ratio of two pure sinusoidal signals, particularly in the context of linear systems where it is desired to represent the gain or loss in amplitude of a single-frequency signal between the input and output. The bel, and its more commonly used submultiple, the decibel, are used with a decadic logarithm (logarithm to the base 10) to measure the ratio of two power-like quantities, such as a mean square signal or a mean square sound pressure in acoustics. Thus two distinctly different quantities are involved. In this review we define the quantities first, without reference to the units, as is standard practice in any system of quantities and units. We show that two different definitions of the quantity power level, or logarithmic power ratio, are possible. We show that this leads to two different interpretations for the meaning and numerical values of the units bel and decibel. We review the question of which of these alternative definitions is actually used, or is used by implication, by workers in the field. Finally, we discuss the relative advantages of the alternative definitions.

On defining base units in terms of fundamental constants

The definitions of the base units of the international system of units have been revised many times since the idea of such an international system was first conceived at the time of the French revolution. The objective today is to define all our units in terms of 'invariants of nature', i.e. by referencing our units to the fundamental constants of physics, or the properties of atoms, rather than the characteristics of our planet or of artefacts. This situation is reviewed, particularly in regard to finding a new definition of the kilogram to replace its present definition in terms of a prototype material artefact.

Definitions of the units radian, neper, bel and decibel

The definition of coherent derived units in the International System of Units (SI) is reviewed, and the important role of the equations defining physical quantities is emphasized in obtaining coherent derived units. In the case of the dimensionless quantity plane angle, the choice between alternative definitions is considered, leading to a corresponding choice between alternative definitions of the coherent derived unit - the radian, degree or revolution. In this case the General Conference on Weights and Measures (CGPM) has chosen to adopt the definition that leads to the radian as the coherent derived unit in the SI. In the case of the quantity logarithmic decay (or gain), also sometimes called decrement, and sometimes called level, a similar choice of defining equation exists, leading to a corresponding choice for the coherent derived unit - the neper or the bel. In this case the CGPM has not yet made a choice. We argue that for the quantity logarithmic decay the most logical choice of defining equation is linked to that of the radian, and is that which leads to the neper as the corresponding coherent derived unit. This should not prevent us from using the bel and decibel as units of logarithmic decay. However, it is an important part of the SI to establish in a formal sense the equations defining physical quantities, and the corresponding coherent derived units.