Synthesis and Structure of Polyoxoanion Supported Organorhodium (I) and Organoiridium (I) Complexes

The iridium 1,5-cyclooctadiene Nb$\sb2$W$\sb4$O$\sb \sp{4-}$ adduct $\{\lbrack({\rm C\sb8H\sb )Ir\rbrack\sb5(Nb\sb2W\sb4O\sb )}\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb3$ (1) has been prepared by reaction of 2.5 eg of $\lbrack{\rm Ir(C\sb8H\sb )(NCCH\sb3)\sb2\rbrack PF\sb6}$ with (Nb$\sb2$W$\sb4$O$\sb )\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb4.$ NMR and IR data suggests the anion of 1 is isostructural with the anion of $\{\lbrack({\rm C\sb7H\sb8)Rh\rbrack\sb{5}(Nb\sb2W\sb4O\sb })\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb3$ (2) reported previously. In 1, two Nb$\sb2$W$\sb4$O$\sb \sp{4-}$ anions act as pentadentate bridging ligands in which both terminal and bridging oxygens are utilized to bind five (C$\sb8$H$\sb $)Ir$\sp+$ units. Reaction of compound 1 with 3 eq of (Nb$\sb2$W$\sb4$O$\sb )\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb4$ in acetonitrile followed by addition of 1 eq of acetic acid results in the formation of $\{\lbrack({\rm C\sb8H\sb )Ir\rbrack\sb2H(Nb\sb2W\sb4O\sb })\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb5$ (3). In the anion of 3, one two-coordinate proton and two four-coordinate (C$\sb8$H$\sb $)Ir$\sp+$ units link together the two Nb$\sb2$W$\sb4$O$\sb \sp{4-}$ anions. The ONb$\sb2$ and ONb oxygens are utilized in binding to the proton and (C$\sb8$H$\sb $)Ir$\sp+$ units respectively. Reaction of $\lbrack{\rm Ir(C\sb8H\sb )(NCCH\sb3)\sb2\rbrack PF}\sb6$ with (P$\sb3$O$\sb9)\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb3$ in methylene chloride has resulted in isolation of $\{\lbrack({\rm C\sb8H\sb )Ir\rbrack(P\sb3O\sb9})\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb2$ (4a). The P$\sb3$O$\sb9\sp{3-}$ anion is bound to iridium in a tridentate fashion making the coordination geometry around Ir$\sp{\rm I}$ approximately square pyramidal.

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

• Main, Deborah Jean

• Chemistry, Inorganic

Identifier

(UMI)AAI8721702

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70374