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The study of ruthenium(II) half-sandwich phosphido complexes containing pentamethylcyclopentadienyl (Cp*) ligand

Previous work in the Rosenberg group showed that the half-sandwich complexes Ru(η5-indenyl)Cl(PR2H)(PPh3) (2i), where R = cyclohexyl (Cy), isopropyl (Pri), phenyl (Ph), para-tolyl (Tolp), react with the strong, bulky base KOBut to give highly reactive complexes Ru(η5-indenyl)(PR2)(PPh3) (6i) containing a ruthenium-phosphorus double bond, Ru=PR2. The reactions of these phosphido complexes 6i with some reagents, such as alkenes, carbon monoxide and dihydrogen, illustrate their rich and varied reactivity. To better understand the mechanisms of these reactions (whether the indenyl effect is necessary), synthesis of analogous secondary phosphine complexes containing the pentamethylcyclopentadienyl (Cp*) ligand, Ru(η5-Cp*)Cl(PPh3)(PR2H) (2) were prepared via ligand substitution at Ru(η5-Cp*)Cl(PPh3)2 (1). Cp* phosphido complexes Ru(η5-Cp*)(PR2)(PPh3) (6) were generated in situ and their reactivity was investigated to see if they behaved similarly to the indenyl complexes. Experimental evidence in this thesis suggests that variable hapticity is not necessary in our indenyl system. In addition, these experimental evidence highlights enhanced lability of ligand at the bulky Cp*Ru fragment and higher Bronsted basicity of the phosphido ligand (PR2-) in Cp* phosphido 6 relative to the indenyl analogues 6i. / Graduate / 2017-12-11 / 0488 / yangjin@uvic.ca

Identiferoai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/7678
Date20 December 2016
CreatorsYang, Jin
ContributorsRosenberg, Lisa
Source SetsUniversity of Victoria
LanguageEnglish, English
Detected LanguageEnglish
TypeThesis
RightsAvailable to the World Wide Web

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