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Rauchfuss, Thomas B. Ogilvy, Ann Elizabeth 2011-05-07T13:13:36Z 2011-05-07T13:13:36Z 10000-01-01 1990 The desulfurization and reduction of the sulfur-containing organic compounds in petroleum products is the objective of catalytic hydrodesulfurization (HDS), one of the largest applications of transition-metal catalysis. However, the specific mechanism for the process is not well understood. This thesis addresses certain aspects of HDS research from an organometallic perspective. A proposed intermediate during thiophene decomposition features thiophene $\sigma$-bound through an $\alpha$-carbon to a surface metal atom. Results from the reaction of ($\rm C\sb5H\sb5$)Fe(CO)(PPh$\sb3$)(2-C$\sb4$H$\sb3$S) and methyl triflate indicate the possible formation of two S-methylated configurational isomers. The first non-mercury containing bimetallic $\mu$-thienyl compound, ((C$\sb5$H$\sb5$)Fe(CO)$\sb2$) $\sb2$(2,5-C$\sb4$H$\sb2$S) was structurally characterized. The reaction of thiophenic compounds with Fe$\sb3$(CO)$\sb{12}$ resulted in metal insertion into the C-S bond. The known benzothiaferrole $\rm Fe\sb2(C\sb8H\sb6S)(CO)\sb6$ (1) was hydrogenated to give an insoluble iron-containing solid and a series of ethylbenzene derivatives. Oxidizing agents convert 1 to the carbonylated heterocycle thiocoumarin. $\rm Fe\sb2$(2-MeC$\sb4$H$\sb3$S)(CO)$\sb6$ desulfurizes to give the corresponding ferrole complex when heated. "$\rm \lbrack (C\sb5 Me\sb5)Rh(TMT)\rbrack\sp{2+}$ (TMT = tetramethylthiophene) reacts with cobaltocene to give the new compound ($\rm C\sb5Me\sb5)Rh(\eta\sp4$-TMT), 2. The $\eta\sp4$-TMT ligand in 2 desulfurizes upon reaction with Fe$\sb3$(CO)$\sb{12}$ to give ($\rm C\sb5Me\sb5)Rh(C\sb4Me\sb4)Fe(CO)\sb3$. An x-ray diffraction study confirms that the Fe(CO)$\sb3$ fragment is included in the $\rm C\sb4Me\sb4$ ring. The thermolysis of 2 resulted in the formation of an ionic compound. The structurally characterized cation consists of four ($\rm C\sb5Me\sb5)Rh(\eta\sp4$-TMT) ""units"" bound to a central rhodium atom in a square planar fashion creating a ""pinwheel"" structure. A new mechanism for thiophene HDS was proposed." (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb6$(CO)$\sb2$ eliminates SCO to give (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb5$(CO). (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb4$ reacts with CO to form (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb4$(CO) (3). This is the first example of a metal-centered ligand addition to a cyclopentadienyl metal sulfide. The x-ray structure of 3 shows a $\rm Ru\sb2S\sb4$ core in a chair conformation with the bridging ($\eta\sp1$-S$\sb2$) ligands in a trans configuration. In the presence of phosphines, (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb4$ reacts with CO to form (($\rm C\sb5Me\sb4Et)Ru$) $\sb2$S$\sb2$(CO)$\sb2$. Made available in DSpace on 2011-05-07T13:13:36Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9021737.pdf: 7105349 bytes, checksum: 21961d6383426492f1f2897f8f320584 (MD5) Previous issue date: 1990 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:51:54Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:23:53-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only AAI9021737 (UMI)AAI9021737 http://hdl.handle.net/2142/21604 eng Copyright 1990 Ogilvy, Ann Elizabeth Chemistry, Inorganic Cyclopentadienyl ruthenium sulfide carbonyls and thiophene activation by iron and rhodium text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.