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Reactions of Pt(IV) and Pd(IV) Complexes with Multi-Electron Substrates

Madduma-Liyanage, Kumudu C
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1416570506

Abstract Details

2014, PhD, University of Cincinnati, Arts and Sciences: Chemistry.
Several square planar d8-electron metal complexes were prepared where the metal center is bonded to a bidentate ligand (L) that is capable of bonding to metal centers in a tridentate, facially coordinating geometry. The complexes undergo cooperative, outer-sphere two-electron transfer to give six-coordinate d6-electron products in which L is tridentate and the sixth coordination site is filled by a solvent-available nucleophile (e.g.,) Br- or ;Cl;-). A main focus of this dissertation research was on the chemistry of the electrochemically generated d6-electron adducts in the presence of potential chemical substrates. These studies indicate that the electrochemically generated d6-electron metal complexes react electrocatalytically with certain organic substrates (e.g.,styrenes). In the best characterized system, the accumulated evidence suggests that the d6-electron complex is reduced back to the d8-electron form by formally transferring a Cl+ ion to the substrate. A survey of a large number of organic substrates suggests that substrate selectivity is under thermodynamic control.In other words, substrates with oxidation potentials higher than those of the d6-electron reagent are not activated, whereas those with lower potentials are activated. In cases where a square planar d8-electron metal complex was used as the substrate, the product was confirmed to be a six-coordinate d6-electron dichloro complex, as expected for Cl+ ion transfer. A detailed analysis of product yields demonstrated that the system was electrocatalytic. In a related study, reactions of a chemically generated tribromo platinum(IV) complex with styrenes were investigated. Several products were identified and rationalized based on a Br+ ion transfer mechanism that does not involve the conventional bromonium ion intermediate found for reactions of olefins with bromine.
William Connick, Ph.D. (Committee Chair)
Ruxandra Dima, Ph.D. (Committee Member)
Hairong Guan, Ph.D. (Committee Member)
118 p.
Inorganic Chemistry
multi-electron transfer; electrocatalysis; chloro- transfer; palladium; platinum

Recommended Citations

Citations

  • Madduma-Liyanage, K. C. (2014). Reactions of Pt(IV) and Pd(IV) Complexes with Multi-Electron Substrates [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1416570506

    APA Style (7th edition)

  • Madduma-Liyanage, Kumudu. Reactions of Pt(IV) and Pd(IV) Complexes with Multi-Electron Substrates. 2014. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1416570506.

    MLA Style (8th edition)

  • Madduma-Liyanage, Kumudu. "Reactions of Pt(IV) and Pd(IV) Complexes with Multi-Electron Substrates." Doctoral dissertation, University of Cincinnati, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1416570506

    Chicago Manual of Style (17th edition)

ucin1416570506
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This open access ETD is published by University of Cincinnati and OhioLINK.