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 Title: Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds Author(s): Hsu, Gishun 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: Treatment of $\rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{3-}$ with PPh$\sb3$ in the presence of two equivalents of $\rm\lbrack Cp\sb2Fe\rbrack\sp+$ under a CO atmosphere provided $\rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-}$. X-ray diffractional studies and $\sp{13}$C NMR studies on $\rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-}$ showed a congested ligand environment. Sunlamp irradiation of $\rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-}$ in the presence of H$\sb2$ gave $\rm\lbrack H\sb2Re\sb6C(CO)\sb{18}\rbrack\sp{2-}$.Treatment of $\rm \lbrack PPN\rbrack\sb3\lbrack Re\sb7C(CO)\sb{21}\rbrack$ with two equivalents of $\rm\lbrack Cp\sb2Fe\rbrack\sp+$ in the presence of diazomethane gave (PPN) (Re$\sb7$C(CO)$\sb{21}$(CH$\sb2$)). Treatment of $\rm\lbrack Re\sb7C(CO)\sb{21}(CH\sb2)\rbrack\sp-$ with acetonitrile gave $\rm\lbrack Re\sb6C(CO)\sb{18}(CH\sb2)\rbrack\sp{2-}$. The methylene ligand in $\rm\lbrack Re\sb7C(CO)\sb{21}(CH\sb2)\rbrack$ and $\rm\lbrack Re\sb6C(CO)\sb{18}(CH\sb2)\rbrack\sp{2-}$ is found bridging a rhenium-rhenium edge. The syntheses of other $\rm\lbrack Re\sb7C(CO)\sb{21}L\rbrack\sp-$ and $\rm \lbrack Re\sb6C(CO)\sb{18}L\rbrack\sp{2-}$ compounds are also discussed.The reaction of $\rm\lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{19}\rbrack$ with Mo(CO)$\sb6$ and $\rm Ru\sb3(CO)\sb{12}$ under photolytic conditions gave $\rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Mo(CO)\sb4\rbrack$ and $\rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Ru(CO)\sb3\rbrack$, respectively. A comparison of the physical properties and reactivity of $\rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Mo(CO)\sb4\rbrack$ and $\rm\lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Ru(CO)\sb3\rbrack$ is described.The reaction of either $\rm\lbrack H\sb2Re\sb6C(CO)\sb{18}\rbrack\sp{2-}$ or $\rm\lbrack HRe\sb6C(CO)\sb{18}\rbrack\sp{3-}$ with (AuPPh$\sb3$)Cl in the presence of DBU gave $\rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-}$. $\rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-}$ reacted with (AuPPh$\sb3$)NO$\sb3$ to give $\rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb4\rbrack$. $\rm \lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-}$ also reacted with $\rm\lbrack Rh(CO)\sb2Cl\rbrack\sb2$ to give $\rm \lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2Rh(CO)\sb2\rbrack\sp-$. Synthesis of other $\rm \lbrack Re\sb6C(CO)\sb{18}ML\sb{n}\rbrack\sp{3-}$ complexes will also be discussed.Treatment of $\rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{3-}$ with one equivalent of $\rm\lbrack Cp\sb2Fe\rbrack\sp+$ gave the $\rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{2-}$ radical, and introduction of tributyltin hydride or a silane gave $\rm\lbrack HRe\sb7C(CO)\sb{21}\rbrack\sp{2-}$. The $\rm \lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{2-}$ radical also reacted with solvents such as acetone or THF, giving $\rm\lbrack HRe\sb7C(CO)\sb{21}\rbrack\sp{2-}$. The nature of the counter ion in the cluster compound and the $\rm\lbrack Cp\sb2Fe\rbrack\sp+$ oxidant also played a role in the reactivity. Issue Date: 1994 Type: Text Language: English URI: http://hdl.handle.net/2142/23004 Rights Information: Copyright 1994 Hsu, Gishun Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9512401 OCLC Identifier: (UMI)AAI9512401
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