Platinum complexes, substitution

Entering group effect platinum complexes substitution reactions, 494 EXAFS spectroscopy cadmium complexes, 929 copper(II) complexes, 720 zinc complexes, 929... 

Lanthanide shift reagents silver complexes, 806 Leaving group effect platinum complexes substitution reactions, 494 Leucine aminopeptidase zinc, 1005 Ligases zinc, 1002... 

Because their rates of substitution tue convenient for study, most work has been done with platinum complexes, and for lhe.se it is found that ligands can be airanged in a fairly consistent order indicating their relative abilities to labilize ligands irans to themselves ... 

Organonickel derivatives also offer cases of the -coordination of the substituted hydrotrisfpyrazol- l-yl)borate ligand. For the palladium and platinum complexes, the M(II) M(IV) (M = Pd, Pt) transformation is facile. Organopalla-dium chemistry offers anew type of agostic interactions, C—H - - - Pd, where the C—H bond belongs to one of the pyrazolate rings. Cyclopalladation of various pyrazol-l-ylborates and -methanes does not modify their structure. 

Square planar complexes of palladium(II) and platinum(II) readily undergo ligand substitution reactions. Those of palladium have been studied less but appear to behave similarly to platinum complexes, though around five orders of magnitude faster (ascribable to the relative weakness of the bonds to palladium). 

Molecules having only a sulfoxide function and no other acidic or basic site have been resolved through the intermediacy of metal complex formation. In 1934 Backer and Keuning resolved the cobalt complex of sulfoxide 5 using d-camphorsulfonic acid. More recently Cope and Caress applied the same technique to the resolution of ethyl p-tolyl sulfoxide (6). Sulfoxide 6 and optically active 1-phenylethylamine were used to form diastereomeric complexes i.e., (-1-)- and ( —)-trans-dichloro(ethyl p-tolyl sulfoxide) (1-phenylethylamine) platinum(II). Both enantiomers of 6 were obtained in optically pure form. Diastereomeric platinum complexes formed from racemic methyl phenyl (and three para-substituted phenyl) sulfoxides and d-N, N-dimethyl phenylglycine have been separated chromatographically on an analytical column L A nonaromatic example, cyclohexyl methyl sulfoxide, did not resolve. 

Kinetics and mechanisms of substitution at Pt(IV) are occasionally mentioned in relation to those complexes which may have anti-tumor properties. An article on molecular modeling of interactions between platinum complexes and nucleotides or DNA includes a brief mention of Pt(IV) (178). 

X Wang, MR Andersson, ME Thompson, and O Inganas, Electrophosphorescence from substituted poly(thiophene) doped with iridium or platinum complex, Thin Solid Films, 468 226-233, 2004. 

In conclusion, nucleophilic substitution by H20, Cl, low- and high-molecular-weight thiols, and other nucleophiles plays a major role in the metabolism of platinum complexes. These reactions direct the activation, deactivation, toxification, detoxification, distribution, and excretion of platinum anticancer drugs. Given the large differences in reactivity, and the multiplicity... 

Nickel complexes are observed to undergo substitution much faster than platinum complexes. Offer an explanation. 

Among the less common oxidation states those of I and III have the most significance. Complexes of platinum(III) have been of interest for many years because of their intermediacy in substitution reactions of platinum(II) and (IV). More recently binuclear platinum(I) and (III) complexes have been isolated, and the chemistry of these new complexes will be of increasing interest in platinum chemistry. Platinum forms strong homometallic bonds giving rise to multimetallic chain compounds and cluster complexes. The increasing use of X-ray crystallography, and 31P and 19 PtNMR will allow systematic studies to be made on these multimetallic platinum complexes. 

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