Oxyligands in triosmium carbonyl cluster compounds

Tridentate triply bridging phosphonate and arsonate clusters of the general formula (μ-H)$\sb2$Os$\sb3$(CO)$\sb9$(μ\sb3, $\eta\sp3$-O$\sb3$ER) (E = P, R = Ph (1), Me; E = As, R = Ph) were prepared. The reaction scheme involved (1) generation of a solution containing a labile cluster species by reaction of H$\sb3$Os$\sb3$(CO)$\sb9$CH with neat trifluoromethanesulfonic (triflic) acid, (2) addition of a large excess of the appropriate free acid, and (3) water quench. A diffraction study of 1 showed the capping PhPO$\sb3$ ligand in a triply bridging tridentate coordination mode. Compound 1 is fluxional, and hydride migration was established as the low barrier dynamic process. Solid/solution structure equivalence for this class of clusters was demonstrated.

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

• Frauenhoff, Greg Robert

Contributors dc:contributor

• Klemperer, Walter G.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1989 Frauenhoff, Greg Robert

Language dc:language

eng

Identifier

AAI8916246
(UMI)AAI8916246

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22589