Biology coordination compounds

In this section, it has been stressed that strain and conflict of interest between the central atom and ligands is often a feature of catalysts. There is reason to believe that this applies in biological systems as well. The ligands in biological coordination compounds are usually very complex, and the subtleties of their conformational requirements can impose strain on the central atom and its immediate environment. Equally, coordination to a central atom can affect the reactivity of the ligand. Some examples will illustrate these points. 

Much effort has been placed in the synthesis of compounds possessing a chiral center at the phosphoms atom, particularly three- and four-coordinate compounds such as tertiary phosphines, phosphine oxides, phosphonates, phosphinates, and phosphate esters (11). Some enantiomers are known to exhibit a variety of biological activities and are therefore of interest Oas agricultural chemicals, pharmaceuticals (qv), etc. Homochiral bisphosphines are commonly used in catalytic asymmetric syntheses providing good enantioselectivities (see also Nucleic acids). Excellent reviews of low coordinate (coordination numbers 1 and 2) phosphoms compounds are available (12). 

Furazano[3,4-/]quinoxaline, 7,8-diphenyl-synthesis, 6, 412 Furazanothiophene synthesis, 6, 417 Furazans, 6, 393-426 biological activity, 6, 425 bond angles, 6, 396 bond lengths, 6, 396 coordination compounds, 6, 403 diamagnetic susceptibilities, 6, 395 dipole moments, 6, 395, 400 heats of combustion, 6, 400 heterocyclic ring reactions, 6, 400-403 IR spectra, 6, 398 isoxazoles from, 6, 81 mass spectra, 6, 399 microwave spectroscopy, 6, 395, 396 MO calculations, 6, 395 monosubstituted... 

Metal complexes of ligands containing a sulfur donor in conjunction with nitrogen, oxygen or a second sulfur have been reviewed in the past [11-13]. For example, reviews of the coordination compounds of dithiophosphates [14], dithiocarbamates [15, 16], dithiolates [17], dithiodiketonates [18], and xanthates [16] have appeared. The analytical aspects [19] and the spectral and structural information of transition metal complexes of thiosemicarbazones [20, 21] have been reviewed previously. Recent developments in the structural nature of metal complexes of 2-heterocyclic thiosemicarbazones and S-alkyldithiocarbazates, depicted below, are correlated to their biological activities. 

At the time of the first volume of CCC(1987), the biological chemistry of cobalt was almost exclusively concerned with the cobalamins. The field has expanded and developed markedly since then. New cobalt-containing proteins have been characterized and applications of traditional cobalt coordination compounds in biology developed. These developments are illustrated below in some detail, as the field was not reviewed in the first edition. 

Some of the important types of coordination compounds occur in biological systems (for example, heme and chlorophyll). There are also significant applications of coordination compounds that involve their use as catalysts. The formation of coordination compounds provides the basis for several techniques in analytical chemistry. Because of the relevance of this area, an understanding of the basic theories and principles of coordination chemistry is essential for work in many related fields of chemistry. In the next few chapters, an introduction will be given to the basic principles of the chemistry of coordination compounds. 

In the last few years, EPR has been widely used to study the electronic structure of four-and five-coordinated low-spin Co(II) complexes. Compounds of this class gained considerable interest because of their relation to biological oxygen carriers and to vitamin B12r. The ground state of the five-coordinated complexes is accepted to be dz2 ), in contrast to the four-coordinated compounds for which the determination of the correct ground state was quite troublesome, due to the fact that these types of Co(II) complexes have low-lying excited states. 

The geometry of the coordination compounds can be similarly predicted based on the coordination number of the central atom. Coordination numbers 2 and 3 are both relatively rare and give linear and planar or pyramidal geometries, respectively. The most important coordination numbers are 4, 5 and 6 with the latter being the most important one as nearly all cations form 6-coordinate complexes. Table 2.4 shows the geometries corresponding to the commonest coordination numbers in biological systems. 

During the last ten years, studies of luminescence and photochemistry of polypyridyl Ru(II), Rh(III) and Co(III) complexes, porphyrins and uranyl salts, in the presence of biological macromolecules such as DNA, have been the focus of increasing research work. The interest in such coordination compounds stems from their easily tunable properties. Not only their size and shape but also their... 

The importance of metal coordination compounds in biological systems has led to the study of polydentate Schilf base complexes of cobalt(II), nickel(II), and copper(II) (204, 205). Dimers have been observed in the spectra of complexes of both tri- and tetradentate ligands [e.g., salicylaldehydeand A,A-bis(salicylidene)ethylenediamine]. The parent ions form the base peaks, and the spectra are characterized... 

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