Synthesis, Structure, and Reactivity of High-Nuclearity Carbido Clusters of Rhenium

The cluster anion (Re$\sb7$C(CO)$\sb{21}\rbrack\sp{3-}$ reacts with late transition metal-based electrophiles to yield the mixed-metal clusters (Re$\sb7$C(CO)$\sb{21}$ML$\sb{\rm n}\rbrack\sp{2-}$ and with H$\sp+$ to yield the hydrido species (HRe$\sb7$C(CO)$\sb{21}\rbrack\sp{2-}$. These complexes have been fully characterized by IR, $\sp1$H NMR, and fast-atom bombardment mass spectroscopies. $\sp1$H and $\sp $C NMR, IR, and cyclic voltammetry studies on selected complexes indicate that the (Re$\sb7$C(CO)$\sb{21}\rbrack\sp{3-}$ cap is a poorer electron donor to the ML$\sb{\rm n}\sp+$ moiety than the cyclopentadienide ligand in the analogous compounds $(\eta\sp5$-C$\sb5$H$\sb5$)ML$\sb{\rm n}$. Variable-temperature $\sp $C NMR studies and X-ray diffraction experiments on several of the mixed-metal clusters demonstrate that each of these compounds adopts a trans-bicapped octahedral configuration of metal atoms, i.e., the ML$\sb{\rm n}$ fragment symmetrically caps the triangular face opposite the unique Re(CO)$\sb3$ group. The compound (HRe$\sb7$C(CO)$\sb{21}\rbrack\sp{2-}$ is a mixture of two isomers, which differ in the position of the hydride ligand on the metal framework.

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

• Henly, Timothy James

Contributors dc:contributor

• Shapley, John R.

• Chemistry, Inorganic

Identifier

(UMI)AAI8815352

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70399