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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 31 (1992), S. 989-1007 
    ISSN: 0570-0833
    Keywords: Chirality ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Since Pasteur's epochal discoveries a century and a half ago, the concept of chirality has continued to play a central role in chemistry and biochemistry. Can chirality be measured? It has long been known that molecular chirality can be given a quantitative meaning through functions specifically parametrized to match the magnitude of pseudoscalar observables. However, chirality is a property that is independent of its physical and chemical manifestations : for a system to be chiral, all that is required is the absence of improper rotations in the symmetry group of the system. This being the case, how can chirality be measured if the “system” is an abstract geometric figure, for example, a scalene triangle in the plane or an asymmetric tetrahedron in three-dimensional space? How does chirality vary as a function of pure shape? In this review we describe recent efforts designed to answer these and related questions.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 33 (1994), S. 823-839 
    ISSN: 0570-0833
    Keywords: Structure elucidation ; Pentacoordinate complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystal structures potentially deliver far more information than is present in the average structural communication - if sufficient structural data on closely related molecules or molecular fragments are available, it may be possible to infer details of geometric changes occurring along certain reaction pathways for the species of interest. This geometric information is extrapolated from an analysis of the similarities between the structures of the fragment in the various crystalline environments, by a method that is now known as structure correlation analysis. Since it was first proposed twenty years ago, the method has been applied to a large variety of chemical systems, but none have received as much attention as the class of five-coordinate compounds. Comparative analyses of the structures of pentacoordinate complexes have yielded information about the intimate mechanisms of substitution and addition/elimination reactions at tetrahedral and square-planar complexes, and about intramolecular isomerizations of five-coordinate compounds. Since its inception, the structure correlation method has gradually adapted techniques from other branches of science, in particular group-theoretical and multivariate statistical techniques, which have been shown to be enormously powerful tools for probing geometrically complex systems. This review traces the development of the method of structure correlation and the evolution of these co-opted techniques, with a specific emphasis on studies of five-coordinate metal complexes.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
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