Phosphorus-containing ruthenacycles: exploring their potential in processes relevant to hydrophosphination.

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dc.contributor.author Morrow, Krista Maria Elena
dc.date.accessioned 2012-04-17T22:24:42Z
dc.date.available 2012-04-17T22:24:42Z
dc.date.copyright 2012 en_US
dc.date.issued 2012-04-17
dc.identifier.uri http://hdl.handle.net/1828/3890
dc.description.abstract Phosphorus-containing metallacycles formed from the [2+2] cycloaddition of unsaturated substrates at the Ru-P π-bond of [Ru(η5-indenyl)(PCy2)(PPh3)] (2) were examined as possible intermediates relevant to hydrophosphination. Reagents, intermediates, products, and by-products involved in the [2+2] cycloaddition were identified and analyzed for reactivity and stability. The products, metallacycles of the form [Ru(η5-indenyl)(κ2-RCHCH2PCy2)(PPh3)] (4), were found to undergo facile cycloreversion. An ethylene η2-coordination adduct was directly observed by low temperature 31P{1H} NMR as an intermediate in the [2+2] cycloaddition mechanism. Steric and electronic effects of alkene substituents on metallacycle formation and selectivity were investigated in detail through rate constant and activation parameter determination, as well as collaborative computational DFT analyses and the construction of a Hammett plot. Preliminary attempts at releasing phosphinated products from ruthenacycle complexes via protonolysis and phosphine substitution were conducted. An unexpected metallacyclic product of one of these attempts, [Ru(η5-indenyl)(κ2-CHCHPCy2)(PPh3)] (10), was identified and characterized. en_US
dc.language.iso en en_US
dc.subject cycloaddition en_US
dc.subject metallacycles en_US
dc.subject ruthenium en_US
dc.subject P ligands en_US
dc.subject hydrophosphination en_US
dc.title Phosphorus-containing ruthenacycles: exploring their potential in processes relevant to hydrophosphination. en_US
dc.type Thesis en_US
dc.contributor.supervisor Rosenberg, Lisa
dc.degree.department Dept. of Chemistry en_US
dc.degree.level Master of Science M.Sc. en_US
dc.rights.temp Available to the World Wide Web en_US
dc.description.scholarlevel Graduate en_US

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