Nuclear magnetic resonance studies of the solution chemistry of metal complexes. XIV. The aqueous chemistry of trimethyllead(IV) and its carboxylic acid complexes

Sayer, Thomas; Backs, Stanley J.; Evans, Christopher A.; Millar, E. K.; Rabenstein, Dallas L.

doi:10.1139/v77-453

Cited by 6 publications

(2 citation statements)

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“…(17). A rough linear free energy relation is observed between complexàtion by (CHj^Pb* and protonation, and this is illustrated in Figure 4.…”

Section: "¥ [15] [(Ch3)2snx(0h2)nfmentioning

confidence: 88%

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The Chemistry of Organometallic Cations in Aqueous Media

Tobias

1979

ACS Symposium Series

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A number of organometallic cations that are at least moderately stable in aqueous solution are known, and among these are the following species: Group IVB, R + ; Group VIIIA, R 3 Pt + . Several of the methyl derivatives, R = CH 3 , can be produced by the action of methanogenic bacteria or by reaction of methylcobalamin with inorganic compounds of the appropriate metal, but data on methylation under environmental conditions are mainly limited to mercury(II). Most of the information available on the aqueous chemistry pertains to the methyl species since these have the highest solubility. Characteristically these ions are sigma-bonded carbanion complexes of the metal in its maximum oxidation state. In 1966, the aqueous chemistry of organometallic cations was reviewed (1), but interest in environmental effects of several of these species in recent years has stimulated a good deal of new work.Although the reactions of metal ions in biological systems are exceedingly complex, a knowledge of the hydrolysis constants and stability constants with a limited number of ligand types will permit a number of predictions about the ionic binding and transport. [In this discussion, unless otherwise indicated, hydrolysis will refer to proton transfer from a coordinated water molecule rather than M-C or M-X bond cleavage in the presence of water.] Thermodynamics will play a large part in governing the reactions of these organometallic species. Without exception, the methyl derivatives are highly labile to substitution at the metal center. In certain cases with bulky alkyl groups, reactions may proceed more slowly because of steric effects. Heterogeneous reactions, e.g. dissolution, are slower with large alkyl groups. Because of their hydrophobic nature, they restrict attack at the metal center. 0-8412-0461-6/78/47-082-130$05.00/0

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“…(17). A rough linear free energy relation is observed between complexàtion by (CHj^Pb* and protonation, and this is illustrated in Figure 4.…”

Section: "¥ [15] [(Ch3)2snx(0h2)nfmentioning

confidence: 88%

“…These spectroscopic techniques should be equally suitable for the study of R3Sn and R2Sn 2+ interactions, and a start already has been made with R3Pb + chemistry (17).…”

Section: Resonances Of Both the Cation Andmentioning

confidence: 99%