Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes

Comstock, Matthew Christian

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Description

Title

Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes

Author(s)

Comstock, Matthew Christian

Issue Date

1996

Doctoral Committee Chair(s)

Shapley, John R.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Chemistry, Inorganic

Language

eng

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.

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Copyright 1996 Comstock, Matthew Christian

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