Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System
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University of Cincinnati / OhioLINK
2011
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=ucin1311773793 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-ucin13117737932021-08-03T06:14:49Z Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System Stace, Justin J. Inorganic Chemistry Organometallic Oxidative Addition Iodine Oxidative Addition Oxidative Addition Kinetics Organometallic Kinetics Rhodium Dimers Rhodium Tetramer Four novel rhodium dimers, [Rh2(dmb)4)(BPh4)2+ (dmb = 2,2dimethyl-1,3-diisocyanopropane), BPh4- = tetraphenyl borate), [Rh2(dmb)4Cl2]Cl2, [Rh2(dmb)4I2](PF6)2 and [Rh2(dmb)2(dppm)2](BPh4)2 (dppm = bis(diphenylphosphinomethane)) are synthesized and characterized to probe the kinetic and mechanistic behavior of a photochromic system formed when [Rh2(dmb)4]2+ is mixed with methyl viologen iodide in acetonitrile. The photochromic species is tentatively identified as a metastable tetrameric complex. An identical tetrameric species is produced during an iodine titration; the instability of the tetramer is discussed. The crystal structures of [Rh2(dmb)4](BPh4)2, [Rh2(dmb)4Cl2]Cl2 and [Rh2(dmb)2(dppm)2](BPh4)2 are presented. The oxidation reaction also yields [Rh2(dmb)4I2]2+ as a final product, in 1:1 stoichiometry. The [Rh2(dmb)2(dppm)2]2+ species does not form a tetrameric complex and is used to study the kinetics and mechanism of the oxidative-addition reaction with iodine. Ionic strength is a complicating factor to understand the kinetics of this oxidation reaction. The mechanism is not fully described by a simple two-step process, but involves complex intermediate(s). Several mechanisms are proposed and discussed.The Pt(dbbpy)(bdt) (dbbpy = 4-4’-dibutyl-2,2’-bipyridine) (bdt = 1,2-dithiolbenzene) complex is synthesized and characterized. The platinum monomer reacts with methyl iodide to yield asymmetric [Pt(dbbpy)(CH3bdt)]I, characterization data is consistent with the methylation of a single sulfur. The crystal structure of Pt(dbbpy)(bdt) and Pt(dbbpy)(bdtO2) are discussed. The kinetics of the reaction and a proposed mechanism are presented. The data agree well with similar experiments (enthalpy and entropy of activation) but there is some disagreement in the literature as to the mechanism(s) that thiol methylation exploit.The synthetic attempt of [Rh2(dmb)4Br2]Br2 and [Rh2(dmb)2(dppe)2]Cl2 (dppe = 1,2-bis(diphenylphosphinoethane)) are presented. Preliminary results of the titration of [Rh2(dmb)4]2+ with bromine and the methylation of [Rh2(dmb)2(dppm)2]2+ by CH3I are discussed. 2011-09-23 English text University of Cincinnati / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=ucin1311773793 http://rave.ohiolink.edu/etdc/view?acc_num=ucin1311773793 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
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NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Inorganic Chemistry Organometallic Oxidative Addition Iodine Oxidative Addition Oxidative Addition Kinetics Organometallic Kinetics Rhodium Dimers Rhodium Tetramer |
| spellingShingle |
Inorganic Chemistry Organometallic Oxidative Addition Iodine Oxidative Addition Oxidative Addition Kinetics Organometallic Kinetics Rhodium Dimers Rhodium Tetramer Stace, Justin J. Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| author |
Stace, Justin J. |
| author_facet |
Stace, Justin J. |
| author_sort |
Stace, Justin J. |
| title |
Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| title_short |
Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| title_full |
Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| title_fullStr |
Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| title_full_unstemmed |
Oxidative-Addition Reactions of Rhodium(I) Dimers and Platinum(II) Monomers; a Study to Understand a Novel Photochromic System |
| title_sort |
oxidative-addition reactions of rhodium(i) dimers and platinum(ii) monomers; a study to understand a novel photochromic system |
| publisher |
University of Cincinnati / OhioLINK |
| publishDate |
2011 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1311773793 |
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AT stacejustinj oxidativeadditionreactionsofrhodiumidimersandplatinumiimonomersastudytounderstandanovelphotochromicsystem |
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