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Title:Synthesis and Structure of Polyoxoanion Supported Organorhodium (I) and Organoiridium (I) Complexes
Author(s):Main, Deborah Jean
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Inorganic
Abstract: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.
The metal dicarbonyl polyoxoanion adducts $\{\lbrack({\rm CO)\sb2Rh\rbrack\sb5(Nb\sb2W\sb4O\sb })\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb3$ (8), $\{\lbrack({\rm CO)\sb2Rh\rbrack\sb3(Nb\sb2W\sb4O\sb })\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb5$ (9), $\{\lbrack({\rm CO)\sb2Ir\rbrack\sb2H(Nb\sb2W\sb4O\sb })\sb2\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb5$ (10), and $\{\lbrack({\rm CO)\sb2Ir\rbrack(P\sb3O\sb9)\}\lbrack(C\sb6H\sb5)\sb3PNP(C\sb6H}\sb5)\sb3\rbrack\sb2$ (11) have been prepared and characterized. Compounds 8, 10, and 11 are synthesized by carbonylation of their respective diene analogs, whereas compound 9 is prepared from (Rh(CO)$\sb2$Cl) $\sb2$ and (Nb$\sb2$W$\sb4$O$\sb )\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb4.$ Based on IR and NMR data, compounds 8, 10, and 11 exhibit the same anion structures as their respective diene analogs.
The novel reaction of $\{\lbrack({\rm C\sb8H\sb )Ir\rbrack(P\sb3O\sb9})\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb2$ (4a) with dioxygen is reported. In 1,2-dichloroethane at 55-60$\sp\circ$, dioxygen reacts with 4a to form $\{\lbrack(\eta\sp1,\eta\sp3{\rm C\sb8H\sb OH)Ir\rbrack(P\sb3O\sb9})\}\lbrack(n$-C$\sb4$H$\sb9)\sb4$N) $\sb2$ (13). A single crystal X-ray diffraction study of 13 shows the Ir$\sp{\rm III}$ atom to be bonded to three oxygens of the P$\sb3$O$\sb9\sp{3-}$ ligand and to four carbons of the C$\sb8$H$\sb $OH ring, making the coordination geometry around iridium octahedral if the allyl function is regarded as occupying two coordination sites. (Abstract shortened with permission of author.)
Issue Date:1987
Description:126 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987.
Other Identifier(s):(UMI)AAI8721702
Date Available in IDEALS:2014-12-15
Date Deposited:1987

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