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dc.contributor.authorBrown, Lorenen
dc.date.accessioned2016-06-20T17:52:45Zen
dc.date.available2016-06-20T17:52:45Zen
dc.date.issued2016-06-16en
dc.identifier.othervt_gsexam:8137en
dc.identifier.urihttp://hdl.handle.net/10919/71373en
dc.description.abstractThe present work describes the design and synthesis of a series of dimers [(η5 - ring)MCl]2(μ2 -Cl)2, (where (η5 -ring)MCl = (η5 -Me4C5R)Rh(III)Cl or (η5 -Me4C5R)Ir(III)Cl). Iridium and rhodium dimeric complexes were synthesized via a microwave reaction and directly compared through single-crystal X-ray crystallography. Finally, the dimeric complexes were evaluated as potential oxidation catalysts. The modified HCp*R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, nheptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,5-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (39 - 98%). Reaction of the HCp*R ligands with [M(COD)](μ2 -Cl)2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) gave the dimeric complexes [Cp*RMCl]2(μ2 -Cl)2 in yields ranging from 16 - 96%. The dimers were characterized by nuclear magnetic resonance (NMR)spectroscopy, single-crystal X-ray diffraction (XRD) (supplemented by powder XRD), high-resolution mass spectrometry (HRMS), and elemental analysis. Complexes studied by XRD were analyzed to understand the bond lengths and bond angles throughout each complex. The dimeric complexes synthesized, will facilitate a complete study on how the R group influences catalytic activity.en
dc.format.mediumETDen
dc.publisherVirginia Techen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectiridium; rhodium; tetramethylcyclopentadiene; microwave; dimer; diene; crystal structure; diol; lactoneen
dc.titleMicrowave-assisted Synthesis of Modified Cyclopentadienyl Iridium and Rhodium Chloro-bridged Dimersen
dc.typeThesisen
dc.contributor.departmentChemistryen
dc.description.degreeMaster of Scienceen
thesis.degree.nameMaster of Scienceen
thesis.degree.levelmastersen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.disciplineChemistryen
dc.contributor.committeechairMerola, Joseph S.en
dc.contributor.committeememberMorris, John R.en
dc.contributor.committeememberYee, Gordon T.en


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