The 'Indenyl Effect' in iridium(I) olefin complexes

"The complexes CpIr($\eta\sp2$-C$\sb8$H$\sb{14}$)CO and ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)CO were prepared in high yield from (($\eta\sp2$-C$\sb8$H$\sb{14}$)$\sb2$Ir(CO)Cl) $\sb2$ and thallium cyclopentadienide or potassium indenide, respectively. The stereoisomers of CpIr($\eta\sp2$-C$\sb8$H$\sb{14}$)CO, ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)CO, and ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)$\sb2$, were characterized by two-dimensional NMR techniques. Due to the ""Indenyl Effect,"" ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)CO was more reactive than CpIr($\eta\sp2$-C$\sb8$H$\sb{14}$)CO toward Lewis bases. The labile cyclooctene ring of ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)CO was readily replaced under mild conditions by other two electron donors such as triphenylphosphine, carbon monoxide, ethylene, or phenylacetylene; CpIr($\eta\sp2$-C$\sb8$H$\sb{14}$)CO was not reactive under identical or more severe conditions. The complex ($\eta\sp5$-C$\sb9$H$\sb7$)Ir($\eta\sp2$-C$\sb8$H$\sb{14}$)CO readily oxidatively added C-Br and Si-H bonds, again under mild conditions, and was found to be an active and robust catalyst for the hydrogenation and hydrosilylation of alkenes and alkynes. The reaction of CO with ($\eta\sp5$-C$\sb9$H$\sb7$)Ir(CO)$\sb2$ resulted in the formation of the $\eta\sp1$-slipped indenyl ring of ($\eta\sp1$-C$\sb9$H$\sb7$)Ir(CO)$\sb3$."

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

• Szajek, Lawrence Philip

Contributors dc:contributor

• Shapley, John R.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1991 Szajek, Lawrence Philip

Language dc:language

eng

Identifier

AAI9211007
(UMI)AAI9211007

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/20881