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Title:Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes
Author(s):Comstock, Matthew Christian
Doctoral Committee Chair(s):Shapley, John R.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Abstract:The reaction of $\rm Ir(CO)\sb2(\eta\sp5$-$\rm C\sb9H\sb7)$ with $\rm Ir(\eta\sp2$-$\rm C\sb2H\sb4)\sb2(\eta\sp5$-$\rm C\sb9H\sb7)$ provided $\rm Ir\sb3(\mu$-$\rm CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$, and the reaction of $\rm Ir(CO)\sb2(\eta\sp5$-$\rm C\sb9H\sb7)$ with $\rm Rh(\eta\sp2$-$\rm C\sb2H\sb4)\sb2(\eta\sp5$-$\rm C\sb9H\sb7)$ provided $\rm Ir\sb{3-x}Rh\sb{x}(\mu$-$\rm CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh$\sb3$ at room temperature to form mononuclear products.
The reaction of $\rm Ir\sb3(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ with HBF$\rm\sb4\cdot Et\sb2$O gave $\rm\lbrack Ir\sb3(\mu$-$\rm H)(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3\rbrack\lbrack BF\sb4$). Subsequent deprotonation led to generation of $\rm C\sb{S}$-$\rm Ir\sb3(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$, which rapidly reverted to an equilibrium mixture containing major isomer $\rm C\sb{3v}$-$\rm Ir\sb3(\mu$-$\rm CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ and minor isomer $\rm C\sb{S}$-$\rm Ir\sb3(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$. Variable temperature NMR experiments indicated that $\rm C\sb{S}$-$\rm Ir\sb3(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ undergoes a dynamic process that involves a third isomer of $\rm Ir\sb3(CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$. This study provides a unique set of relative energies in solution for three of the four observed forms for a $\rm M\sb3(CO)\sb3(\eta\sp5$-$\rm L)\sb3$ system.
The reactions of $\rm C\sb{3v}$-$\rm Ir\sb3(\mu$-$\rm CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ with metal fragment electrophiles containing Cu, Ag, Au, or Hg provided cationic tetranuclear clusters, which show a rearrangement of the $\rm Ir\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3$ moiety to a $\rm C\sb{S}$ geometry. The reaction with TIPF$\sb6$ gave $\rm\lbrack Ir\sb3Tl(\mu$-$\rm CO)\sb3(\eta\sp5$-$\rm C\sb9H\sb7)\sb3\rbrack\lbrack PF\sb6$), which maintains $\rm C\sb{3v}$ geometry and has the thallium ion encapsulated by the six-membered rings of the indenyl ligands.
The reaction of $\rm Ir(CO)(\eta\sp2$-$\rm C\sb8H\sb{14})(\eta\sp5$-$\rm C\sb9H\sb7)$ with $\rm Re\sb2(\mu$-$\rm H)\sb2(CO)\sb8$ formed the mixed-metal cluster $\rm IrRe\sb2(\mu$-$\rm H)\sb2(CO)\sb9(\eta\sp5$-$\rm C\sb9H\sb7)$. Deprotonation with KOH/EtOH and addition of (PPN) (Cl) provided $\rm\lbrack PPN\rbrack\lbrack IrRe\sb2(\mu$-$\rm H)(CO)\sb9(\eta\sp5$-$\rm C\sb9H\sb7)$). Addition of PPh$\sb3$ to $\rm IrRe\sb2(\mu$-$\rm H)\sb2(CO)\sb9(\eta\sp5$-$\rm C\sb9H\sb7)$ led to the carbonyl substitution product $\rm IrRe\sb2(\mu$-$\rm H)\sb2(CO)\sb8(PPh\sb3)(\eta\sp5$-$\rm C\sb9H\sb7)$, which contains the phosphine ligand on a rhenium atom, as well as to cluster fragmentation.
The reactions of $\rm Ir(CO)(\eta\sp2$-$\rm C\sb8H\sb{14})(\eta\sp5$-$\rm C\sb9H\sb7)$ with $\rm C\sb2R\sb2$ led to $\rm Ir(CO)(\eta\sp2$-$\rm C\sb2R\sb2)(\eta\sp5$-$\rm C\sb9H\sb7)$ and $\rm Ir\sb2(CO)\sb2(\mu$-$\rm C\sb2R\sb2)(\eta\sp5$-$\rm C\sb9H\sb7)\sb2$ (R = Ph, Tol). Also, alkyne coupling and activation of a C-H bond in the arene solvent formed a novel mononuclear compound containing a substituted butadiene ligand.
Issue Date:1996
Type:Text
Language:English
URI:http://hdl.handle.net/2142/20150
ISBN:9780591197792
Rights Information:Copyright 1996 Comstock, Matthew Christian
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9712238
OCLC Identifier:(UMI)AAI9712238


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