Ligand Substitution Dynamics

Substitution of a ligand in an inner sphere complex by an outside group is the most fundamental reaction in metal ion chemistr

Noninnocence in Metal Complexes: A Dithiolene Dawn

Noninnocence in inorganic chemistry traces its roots back half a century to work that was done on metal complexes containing unsaturated dithiolate ligands. In a flurry of activity in the early 1960s by three different research groups, homoleptic bis and tris complexes of these ligands, which came to be known as dithiolenes, were synthesized, and their structural, electrochemical, spectroscopic, and magnetic properties were investigated. The complexes were notable for facile one-electron transfers and intense colors in solution, and conventional oxidation-state descriptions could not account for their electronic structures. The bis complexes were, in general, found to be square-planar, including the first examples of this geometry for paramagnetic complexes and different formal dn configurations. Several of the neutral and monoanionic tris complexes were found to have trigonal-prismatic coordination, the first time that this geometry had been observed in molecular metal complexes. Electronic structural calculations employing extended Hückel and other semiempirical computational methods revealed extensive ligand–metal mixing in the frontier orbitals of these systems, including the observation of structures in which filled metal-based orbitals were more stable than ligand-based orbitals of the same type, suggesting that the one-electron changes upon oxidation or reduction were occurring on the ligand rather than on the metal center. A summary of this early work is followed with a brief section on the current interpretations of these systems based on more advanced spectroscopic and computational methods. The take home message is that the early work did indeed provide a solid foundation for what was to follow in investigations of metal complexes containing redox-active ligands

A novel method to construct stationary solutions of the Vlasov-Maxwell system : the relativistic case

A method to derive stationary solutions of the relativistic Vlasov-Maxwell system is explored. In the non-relativistic case, a method using the Hermite polynomial series to describe the deviation from the Maxwell-Boltzmann distribution is found to be successful in deriving a few stationary solutions including two dimensional one. Instead of the Hermite polynomial series, two special orthogonal polynomial series, which are appropriate to expand the deviation from the Maxwell-J\"uttner distribution, are introduced in this paper. By applying this method, a new two-dimensional equilibrium is derived, which may provide an initial setup for investigations of three-dimensional relativistic collisionless reconnection of magnetic fields.Comment: 15pages, 2 figures, to appear in Phys. Plasma

Hydrodynamic air lubricated compliant surface bearing for an automotive gas turbine engine. 2: Materials and coatings

Material coatings for an air-lubricated, compliant journal bearing for an automotive gas turbine engine were exposed to service test temperatures of 540 C or 650 C for 300 hours, and to 10 temperature cycles from room temperatures to the service test temperatures. Selected coatings were then put on journal and partial-arc foils and tested in start-stop cycle tests at 14 kPa (2 psi) loading for 2000 cycles. Half of the test cycles were performed at a test chamber service temperature of 540 C (1000 F) or 650 C (1200 F); the other half were performed at room temperature. Based on test results, the following combinations and their service temperature limitations are recommended: HL-800 TM (CdO and graphite) on foil versus chrome carbide on journal up to 370 C (700 F); NASA PS 120 (Tribaloy 400, silver and CaF2 on journal versus uncoated foil up to 540 C (1000 F); and Kaman DES on journal and foil up to 640 C (1200 F). Kaman DES coating system was further tested successfully at 35 kPa (5 psi) loading for 2000 start-stop cycles

Ligand Substitution Processes

From the preface: The subject of the mechanistic study of ligand substitution reactions is currently undergoing an exciting growth. New fast-reaction techniques have removed the upper limit on rates that can be measured, and extension to less familiar central metal atoms has begun in earnest. This might seem the wrong moment for review of the field. As yet, definitive treatment is possible only for those complexes involving monodentate ligands with cobalt(III) and platinurn(II). But, because information is so extensive for these systems, it is clear that they are functioning as models from which concepts and experiments are generated for application over the fast-growing range of the subject. We believe that this is an important moment to reopen debate on fundamentals so that concepts will be most felicitously formulated to aid growth of understanding. This monograph is centrally concerned with three aspects of those fundamentals. We have attempted to develop an approach to classification of ligand substitution reactions that is adapted to what seem to have emerged as the characteristic features of these reactions and is susceptible to operational tests. (We do recognize that any such scheme of ideas is necessarily obsolescent once it is formulated since new experiments will certainly follow immediately.) We have tried to evaluate the basis for making generalizations about ligand substitution processes and to formulate tests to show whether new reactions fall within familiar patterns. Finally, we have sought to base the models of ligand substitution processes in the language of molecular-orbital theory. We believe that MO theory is most useful, because it may be used to correlate rate data on complexes with the extensive information available from spectral and magnetic studies, yet differs from crystal-field theory in providing a natural place for consideration of the bonding electrons, which must be a principal determinant of reaction processes. To keep this essay within bounds, we assume familiarity with the elements of experimental kinetics, transition-state theory, and the simple molecular-orbital theory of complexes. Introductory physical chemistry, some familiarity with the study of reaction mechanisms, and mastery of one of the qualitative treatments of MO theory as applied to transition-metal complexes should provide sufficient background. Thus, we hope that this book will be useful to students, relatively early in their careers, who wish to explore this field. Our debts to very many workers will be obvious throughout. We want to record here our special personal debt to Professors Ralph G. Pearson and Fred Basolo and to Dr. Martin Tobe. We particularly thank Professor George S. Hammond for his interest and enthusiasm in this project. Professor Hammond carefully read and criticized the entire manuscript in the final drafts. We received many other valuable criticisms at various stages of this project from Professors R. D. Archer, F. Basolo, J. O. Edwards, J. Finholt, P. Haake, J. Halpern, A. Kropf, R. G. Pearson, S. I. Shupack, M. S. Silver, and C. Walling, and Dr. U. Belluco and Dr. L. Cattalini. We very much appreciate their help and probably should have followed their suggestions more closely. We warmly acknowledge expert assistance from Mrs. Madeline deFriesse, Miss Jan Denby, and Mrs. Diane Celeste in preparation of the manuscript. COOPER H. LANGFORD HARRY B. GRAY Amherst, Massachusetts New York, New York October 196

Effect of weightlessness and radiation on the growth of the wheat coleoptile for the purpose of defining and verifying an experiment suitable for use in a biosatellite

Effects of temperature, X-ray irradiation, and elevated gravity on wheat seedling growt

Enforcement of pollution regulations in a declining industry

An examination of the effect of EPA enforcement activity as it relates to company plant-closing decisions and company compliance decisions in the U.S. steel industry, finding fewer enforcement actions taken toward plants with an already high probability of closing.Steel industry and trade ; Pollution

Are OSHA Health Inspections Effective? A Longitudinal Study in the Manufacturing Sector

We examine the impact of OSHA health inspections on compliance with agency regulations in the manufacturing sector, with a unique plant-level dataset of inspection and compliance behavior during 1972-1983, the first twelve years of OSHA enforcement operations. Two major findings are robust across the range of linear and count models estimated in the paper: (1) the number of citations and the number of violations of worker exposure restrictions decrease with additional health inspections in manufacturing plants; and (2) the first health inspection has the strongest impact. The results suggest that prior research focusing on the limited impact of OSHA safety regulations may under-estimate OSHA's total contribution to reducing workplace risks.

The Declining Effects of OSHA Inspections on Manufacturing Injuries: 1979 to 1998

This study compares the impact of OSHA inspections on manufacturing industries using data from three time periods: 1979-85, 1987-91, and 1992-98. We find substantial declines in the impact of OSHA inspections since 1979-85. In the earliest period we estimate that having an OSHA inspection that imposed a penalty reduces injuries by about 15%; in the later periods it falls to 8% in 1987-91 and to 1% (and statistically insignificant) in 1992-98. Testing for different effects by inspection type, employment size, and industry, we find differences across size classes, but these cannot explain the overall decline. In fact, we find reductions in OSHA's impact over time for nearly all subgroups we examine, so shifts across subgroups cannot explain the whole decline. We examine various other hypotheses concerning the declining impact, but in the end we are not able to provide a clear explanation for the decline.