title: Synthesis and structures of cadmium carboxylate and thiocarboxylate compounds with a sulfur-rich coordination environment: carboxylate exchange kinetics involving tris(2-mercapto-1-t-butylimidazolyl)hydroborato cadmium complexes, [Tm(Bu(t))]Cd(O2CR).
abstract: A series of cadmium carboxylate compounds in a sulfur-rich environment provided by the tris(2-tert-butylmercaptoimidazolyl)hydroborato ligand, namely, [Tm(Bu(t))]CdO2CR, has been synthesized via the reactions of the cadmium methyl derivative [Tm(Bu(t))]CdMe with RCO2H. Such compounds mimic aspects of cadmium-substituted zinc enzymes and also the surface atoms of cadmium chalcogenide crystals, and have therefore been employed to model relevant ligand exchange processes. Significantly, both (1)H and (19)F NMR spectroscopy demonstrate that the exchange of carboxylate groups between [Tm(Bu(t))]Cd(κ(2)-O2CR) and the carboxylic acid RCO2H is facile on the NMR time scale, even at low temperature. Analysis of the rate of exchange as a function of concentration of RCO2H indicates that reaction occurs via an associative rather than dissociative pathway. In addition to carboxylate compounds, the thiocarboxylate derivative [Tm(Bu(t))]Cd[κ(1)-SC(O)Ph] has also been synthesized via the reaction of [Tm(Bu(t))]CdMe with thiobenzoic acid. The molecular structure of [Tm(Bu(t))]Cd[κ(1)-SC(O)Ph] has been determined by X-ray diffraction, and an interesting feature is that, in contrast to the carboxylate derivatives [Tm(Bu(t))]Cd(κ(2)-O2CR), the thiocarboxylate ligand binds in a κ(1) manner via only the sulfur atom.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Ava
authors.initials: A
authors.lastname: Kreider-Mueller
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Quinlivan
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Jonathan S
authors.initials: JS
authors.lastname: Owen
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Gerard
authors.initials: G
authors.lastname: Parkin
mesh_terms: D019187:Cadmium Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
chemical_list: D019187:Cadmium Compounds; D002264:Carboxylic Acids; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D013455:Sulfur
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