The Chemistry of Triruthenium Hydrocarbyls (Metal Clusters)

The triruthenium methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), was prepared by a hydride addition/protonation sequence from HRu(,3)(CO)(,10)((mu)-COCH(,3)). Variable temperature ('1)H and ('13)C NMR experiments suggest the intermediacy of a formyl complex, presumably HRu(,3)(CO)(,9)(C(H)O)((mu)-COCH(,3))('-) , in the preparation of HRu(,3)(CO)(,10)((mu)(,3)-CH). The methylidyne cluster, HRu(,3)(CO)(,10)((mu)(,3)-CH), rearranges rapidly (-10(DEGREES)C) to the isomeric carbonylmethylidyne cluster, H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO), via intramolecular coupling of the carbyne ligand and a cluster-bound carbonyl. Hydrogenation of H(,2)Ru(,3)(CO)(,9)((mu)(,3)-CCO) yields H(,3)Ru(,3)(CO)(,9)((mu)(,3)-CH), demonstrating that this C-C coupling process is reversible.

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

2014

Author dc:creator

• Holmgren, Jennifer Salem

• Chemistry, Inorganic

Identifier

(UMI)AAI8610940

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70317