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oai:www.ideals.illinois.edu:2142/84312 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Girolami, Gregory S. Jew, Richard L. 2015-09-25T22:13:54Z 2015-09-25T22:13:54Z 10000-01-01 2008 2008 To understand these variances, the molecular geometries of several osmium(II) and osmium(IV) complexes were investigated. (C5H5)Os(dmpm)Br reacts with NaOMe in refluxing methanol to afford the monohydride compound (C5H5)Os(dmpm)H, which can be protonated with HBF 4·Et2O to afford [(C5H5)Os(dmpm)H 2][BF4]. Comparison of the X-ray crystal structures of (C 5H5)Os(dmpm)H and (C5Me5)Os(dmpm)H revealed no significant differences. In contrast, comparison of the structures of [(C5H5)Os(dmpm)H2+] and [(C5Me5)Os(dmpm)H2+] showed that C5Me5 is more sterically demanding than C 5H5, as evidenced by the 7--8° decrease in the dihedral angle between the P-Os-P and C5 ring planes for the C5H 5 analogue, suggesting that movement of the phosphine toward the less sterically bulky C5 ring may lead to greater distances between cisoid ligands, effectively raising the barrier to hydrogen exchange in the dihydride and the methyl hydride systems. Made available in DSpace on 2015-09-25T22:13:54Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3337810.pdf: 1843547 bytes, checksum: 09f9c70b4a986e4cd0ee9a4e6308a6b6 (MD5) Previous issue date: 2008 Embargo set by: Seth Robbins for item 85593 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 140 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2008. http://hdl.handle.net/2142/84312 (MiAaPQ)AAI3337810 eng Chemistry, Inorganic Steric and Electronic Effects Induced by Ancillary Ligand Substitutions on Cyclopentadienyl Osmium Complexes text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.