Microwave-assisted Synthesis of Modified Cyclopentadienyl Iridium and Rhodium Chloro-bridged Dimers
| dc.contributor.author | Brown, Loren | en |
| dc.contributor.committeechair | Merola, Joseph S. | en |
| dc.contributor.committeemember | Morris, John R. | en |
| dc.contributor.committeemember | Yee, Gordon T. | en |
| dc.contributor.department | Chemistry | en |
| dc.date.accessioned | 2016-06-20T17:52:45Z | en |
| dc.date.available | 2016-06-20T17:52:45Z | en |
| dc.date.issued | 2016-06-16 | en |
| dc.description.abstract | The 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.description.degree | Master of Science | en |
| dc.format.medium | ETD | en |
| dc.identifier.other | vt_gsexam:8137 | en |
| dc.identifier.uri | http://hdl.handle.net/10919/71373 | en |
| dc.publisher | Virginia Tech | en |
| dc.rights | In Copyright | en |
| dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
| dc.subject | iridium | en |
| dc.subject | rhodium | en |
| dc.subject | tetramethylcyclopentadiene | en |
| dc.subject | microwave | en |
| dc.subject | dimer | en |
| dc.subject | diene | en |
| dc.subject | crystal structure | en |
| dc.subject | diol | en |
| dc.subject | lactone | en |
| dc.title | Microwave-assisted Synthesis of Modified Cyclopentadienyl Iridium and Rhodium Chloro-bridged Dimers | en |
| dc.type | Thesis | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
| thesis.degree.level | masters | en |
| thesis.degree.name | Master of Science | en |
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