Metal complexes with phenols

Simple organic molecules such as small carboxylic acids (oxalate, acetate, malonate, citrate, etc.), amino acids and phenols are all ligands for metals. Such compounds may all occur as degradation products of organic matter in natural waters. The complexes formed are typically charged hydrophilic complexes. The stability of the metal complexes with these ligands is, however, moderate in most cases. Model calculations including such compounds at realistic concentrations indicate that their effects on speciation are relatively small [29],... 

Rates of ligand exchange depend quite strongly on the coordina-tive environment of the metal center. The water exchange rate of Fe(H2O)5(OH)is almost three orders of magnitude higher than that of Fe(H20)g+, and follows a dissociative, rather than an associative exchange mechanism (20). Fe(1120)5(OH)has also been shown to form inner-sphere complexes with phenols (27), catechols (28), and a-hydroxycarboxylic acids (29) much more quickly than Fe(H20) +. The mechanism for complex formation with phenolate anion (A-) is shown below (27) ... 

In general, the introduction of spatially hindered phenols into coordination compounds may produce stable free-radical forms [138b—140]. A series of metal complexes with redox ligands, containing derivatives of 2,6-di-t-butylphenols n- or a-connected, or vicinal fragments in the coordination environment of the central metal atom, were synthesized in this way 7i-aryl [141], Tt-cr-allyl [142] compounds, nitrile complexes [143], metal glioximates [144], salicylaldiminates [145,146], por-phyrines [147-149], and phthalocyanines [150,151],... 

Transition metal ions with organic radicals exist in the active sites of metalloproteins. The best understood example is galactose oxidase, which features a single Cu(II) ion coordinated to a modified tyrosyl radical. Many combined experimental and theoretical studies have focused on electronic properties of metal complexes with redox active ligands, yet reactivity beyond characterization has been limited. We will demonstrate the influence of the metal complex redox state on H2 activation by anilino-phenolate noninnocent ligands. 

Phenolic Dispersions. These systems are predominantly resin-in-water systems in which the resin exists as discrete particles. Particle size ranges from 0.1 to 2 p.m for stable dispersions and up to 100 p.m for dispersions requiring constant agitation. Some of the earliest nonaqueous dispersions were developed for coatings appHcations. These systems consist of an oil-modified phenoHc resin complexed with a metal oxide and a weak solvent. 

Platinum-group metals (qv) form complexes with chelating polymers with various 8-mercaptoquinoline [491-33-8] derivatives (83) (see Chelating agents). Hydroxy-substituted quinolines have been incorporated in phenol—formaldehyde resins (84). Stannic chloride catalyzes the condensation of bis(chloromethyl)benzene with quinoline (85). 

Manufacture of alkylsulfones, important intermediates for metal-complex dyes and for reactive dyes, also depends on O-alkylation. An arylsulphinic acid in an aqueous alkaline medium is treated with an alkylating agent, eg, alkyl haUde or sulfate, by a procedure similar to that used for phenols. In the special case of P-hydroxyethylsulfones (precursors to vinylsulfone reactive dyes) the alkylating agent is ethylene oxide or ethylene chlorohydrin. 

Attempts have been made to catalyze the arrangement of 3-oxaquadricyclane to oxepins with transition-metal complexes.1 32 1 35 When dimethyl 2,4-dimethyl-3-oxaquadricyclane-l,5-dicarboxylate is treated with bis(benzonitrile)dichloroplatinum(II) or dicarbonylrhodium chloride dimer, an oxepin with a substitution pattern different from that following thermolysis is obtained as the main product. Instead of dimethyl 2,7-dimethyloxepin-4,5-dicarboxylate, the product of the thermal isomerization, dimethyl 2,5-dimethyloxepin-3,4-dicarboxylate (12), is formed due to the cleavage of a C O bond. This transition metal catalyzed cleavage accounts also for the formation of a 6-hydroxyfulvene [(cyclopentadienylidene)methanol] derivative (10-15%) and a substituted phenol (2-6%) as minor products.135 The proportion of reaction products is dependent on solvent, catalyst, and temperature. 

The methylxanthines vary in their ability to form certain metal complexes. For example, theophylline will complex with both copper and silver whereas caffeine will not.16 The interpretation of this is that the metal ion forms a pentacyclic complex involving the phenolic 0 at C-6 and N at 7.18... 

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