Studies of the mechanism of oxygen atom transfer from molecular oxygen to iridium-coordinated cyclooctadiene

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Lockledge, Scott Potter

Contributors dc:contributor

• Klemperer, Walter G.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1990 Lockledge, Scott Potter

Language dc:language

eng

Identifier

AAI9114327
(UMI)AAI9114327

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/21894