Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds

Hsu, Gishun

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Description

Title

Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds

Author(s)

Hsu, Gishun

Issue Date

1994

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

• 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.

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text

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Copyright 1994 Hsu, Gishun

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