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Klemperer, Walter G. Lockledge, Scott Potter 2011-05-07T13:22:26Z 2011-05-07T13:22:26Z 10000-01-01 1990 The cyclooctadiene complex ((C$\sb8$H$\sb{12}$)Ir(P$\sb3$O$\sb9$)) ((n-C$\sb4$H$\sb9$)$\sb4$N) $\sb2$, a, reacted in solution at ambient temperature with O$\sb2$ to form ((C$\sb8$H$\sb{11}$OH)Ir(P$\sb3$O$\sb9$)) ((n-C$\sb4$H$\sb9$)$\sb4$N) $\sb2$, f. Sealed tube $\sp{31}$P NMR spectroscopic experiments established the presence of three additional species in this reaction and the relationship between them. One of these intermediates, the oxametallacyclobutane complex ((C$\sb8$H$\sb{12}$O)Ir(P$\sb3$O$\sb9$)) ((n-C$\sb4$H$\sb9$)$\sb4$N) $\sb2$, e, was isolated and structurally characterized. Pseudo-octahedral coordination geometry at the Ir(III) center is defined by three terminal (P$\sb3$O$\sb9$)$\sp{3-}$ oxygen atoms, an olefinic C=C bond, and the carbon and oxygen atoms of an oxametallacyclobutane ring. The structures a and e are related by insertion of an O atom into a C-Ir bond of a. The structures of e and f are related by proton transfer from the allylic carbon of e to the oxygen atom of the oxametallacyclobutane ring. Oxygen uptake experiments indicated that both atoms of O$\sb2$ are incorporated into a molecule of a. Two other species were observed by $\sp{13}$C and $\sp{31}$P NMR spectroscopy and structures for these complexes are proposed. On the basis of these observations, a mechanism is proposed detailing the incorporation of the oxygen atoms from O$\sb{2}$ into a and its subsequent reactivity. Made available in DSpace on 2011-05-07T13:22:26Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114327.pdf: 3890413 bytes, checksum: e1723df5b022b6579aeb0d9397f73ea5 (MD5) Previous issue date: 1990 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:55Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:24:59-05:00 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 AAI9114327 (UMI)AAI9114327 http://hdl.handle.net/2142/21894 eng Copyright 1990 Lockledge, Scott Potter Chemistry, Inorganic Studies of the mechanism of oxygen atom transfer from molecular oxygen to iridium-coordinated cyclooctadiene text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.