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Shapley, John R. Comstock, Matthew Christian 2011-05-07T12:30:24Z 2011-05-07T12:30:24Z 10000-01-01 1996 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. Made available in DSpace on 2011-05-07T12:30:24Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712238.pdf: 5994804 bytes, checksum: c9b52ac7f8282a3f1f65f3451a2bc2c4 (MD5) Previous issue date: 1996 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:54Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:18:11-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only 9780591197792 AAI9712238 (UMI)AAI9712238 http://hdl.handle.net/2142/20150 eng Copyright 1996 Comstock, Matthew Christian Chemistry, Inorganic Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.