Exchange reactions paramagnetic metal complexes

Electron paramagnetic resonance (continued) cobalt-thermolysin complex, 28 334, 335 exchange reactions, 31 106-107 glutamine synthetase, 28 358-364 invisible oxygen species, 31 94-95 metalloenzymes, 28 324, 326 metal particle size distribution, 36 99-100, 104... 

Catalysis by transition metal complexes and metaUoenzymes involves a sequence of ligand exchange reactions. Such a reaction can he viewed as an interchange of an inner sphere and outer sphere ligand. It is argued therefore that the structure of the second coordination sphere is of direct relevance to catalysis. A method of studying second coordination sphere structure based on dipolar NMR shifts in paramagnetic complexes is discussed. Even in weakly bound complexes, there is a definite preferred structure for the complex which may or may not be favorable for a subsequent substitution reaction. 

At the beginning of this section we mentioned that O/P conversion may occur at a paramagnetic centre, while H/D exchange may occur via homolytic or heterolytic splitting of the H—H bond. We may form a paramagnetic as well as polar centre by treating an electron donor with an electron acceptor, forming an electron-donor-acceptor complex. This can be illustrated for the simple case of the reaction between sodium metal and naphthalene ... 

Copper(II) and zinc(II) are two of the more labile divalent metal ions and as a consequence the former is too labile for its water exchange rate to be determined by the NMR methods which utilize the paramagnetism of other divalent first-row transition metal ions, while the latter is diamagnetic and such NMR methods cannot be applied. However, it has been shown that water exchange rates and mechanisms can be deduced with reasonable reliability from simple ligand substitution studies, and this is one of the reasons for a recent variable-pressure spec-trophotometric SF study of the substitution of 2-chloro-l,10-phenanthroline on Cu(II) and Zn(II). The observed rate constants for the complexation reaction (kc) and the decomplexation reaction (k ) and their associated activation parameters for Cu(II) and Zn(II) are kc(298 K) = 1.1 x 10 and 1.1 x 10 dm mol" s", AH = 33.6 and 37.9 kJ mol", A5 = 3 and -2JK- mol", AV = 7.1 and 5.0 cm" mol", k 29S K) = 102 and 887 s", AH = 60.6 and 57.3 kJ mol", A5 = -3 and 4 J K" mol" and A V = 5.2 and 4.1 cm" mol". These data are consistent with the operation of an mechanism for the rate-determining first bond formation by 2-chloro-l,10-phenanthroline with the subsequent chelation step being faster [Eq. (18)]. For this mechanistic sequence (in which [M(H20)6 L-L] is an outer-sphere complex) it may be shown that the relationships in Eq. (19) apply. 

Delocalization of c -electron spin from a transition metal has been used to study structure, equilibria, and reactions of complexes, particularly ligand exchange and solvation. Other applications are to organometallics, such as metallocenes, metallobiomolecules such as porphyrins (haemoglobins, cytochromes), iron-sulfur clusters, and so on. Organic radicals such as nitroxides or aromatic radical ions are useful spin probes also. The field of paramagnetic NMR spectroscopy has been reviewed biennially. ... 

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