The reaction of TlCl$\sb3\cdot$4H$\sb2$O with a methanolic KOH solution of Fe(CO)$\sb5$ is known to produce $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb4(CO)\sb{16}\rbrack$ which serves as a precursor for several Tl-Fe carbonyl compounds. When a solution of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb4(CO)\sb{16}\rbrack$ is allowed to stand in the sunlight for long periods of time, three new thallium-iron carbonyls are also known to result: $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb6(CO)\sb{24}\rbrack$, $\lbrack\rm Et\sb4N\rbrack\sb4\lbrack Tl\sb4Fe\sb8(CO)\sb{30}\rbrack$ and $\lbrack\rm Et\sb4N\rbrack\sb6\lbrack Tl\sb6Fe\sb{10}(CO)\sb{36}\rbrack$. $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb6(CO)\sb{24}\rbrack$ may be synthesized by oxidation of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb4(CO)\sb{16}\rbrack$ with $\lbrack\rm Cu(MeCN)\sb4\rbrack\lbrack BF\sb4\rbrack$ or by placing a solution of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb4(CO)\sb{16}\rbrack$ or $\lbrack\rm Et\sb4N\rbrack\lbrack (tmeda)TlFe\sb2(CO)\sb8\rbrack$ and Fe(CO)$\sb5$ in the sunlight. $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb4(CO)\sb{16}\rbrack$ also reacts with various bidentate Lewis bases (L) to form adducts of general formula $\lbrack\rm Et\sb4N\rbrack\lbrack (L)TlFe\sb2(CO)\sb8\rbrack$, several of which have been structurally characterized. The indium analogues of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack Tl\sb2Fe\sb6(CO)\sb{24}\rbrack$ and $\lbrack\rm Et\sb4N\rbrack\lbrack (L)TlFe\sb2(CO)\sb8\rbrack$ have been synthesized by addition of InCl$\sb3$ to K (HFe(CO)$\sb4$), and addition of Lewis bases to $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack In\sb2Fe\sb4(CO)\sb{16}\rbrack$, respectively. The photolysis of a solution of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack In\sb2Fe\sb4(CO)\sb{16}\rbrack/Fe(CO)\sb5$ also affords $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack In\sb2Fe\sb6(CO)\sb{24}\rbrack$.
The reaction of PbCl$\sb2$ with a methanolic KOH/Fe(CO)$\sb5$ solution produces two compounds, depending upon the ratio of starting reagents used: $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack PbFe\sb4(CO)\sb{16}\rbrack$ and $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack Pb\{Fe(CO)\sb4\}\sb3\rbrack$. Similarly, $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack Sn\{Fe(CO)\sb4\}\sb3\rbrack$ is synthesized by reaction of SnCl$\sb2$ with K (HFe(CO)$\sb4\rbrack$. A variable temperature $\sp{13}$C-NMR study of $\lbrack\rm Et\sb4N\rbrack\sb2\lbrack EFe\sb4(CO)\sb{16}\rbrack$, E = Sn, Pb, $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack Pb\{Fe(CO)\sb4\}\sb3\rbrack$ and PbFe$\sb4$(CO)$\sb{16}$ has been undertaken in order to understand the rearrangement processes of the carbonyl ligands occurring in solution. The single crystal X-ray structures of $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack SnFe\sb4(CO)\sb{16}\rbrack$ and $\lbrack \rm Et\sb4N\rbrack\sb2\lbrack E\{Fe(CO)\sb4\}\sb3\rbrack$, E = Sn, Pb, are also reported.
The reduction of Ph$\sb2$BiCl with two equivalents of sodium in liquid NH$\sb3$ followed by addition of Fe(CO)$\sb5$ yields two main products, $\lbrack \rm PhBiFe(CO)\sb4\rbrack\sb2$ and (Ph$\sb2$Bi)$\sb2$Fe(CO)$\sb4$, along with traces of Ph$\sb4$Bi$\sb2$. Evidence supports (Ph$\sb2$Bi)$\sb2$Fe(CO)$\sb4$ as an intermediate in the formation of $\lbrack \rm PhBiFe(CO)\sb4\rbrack\sb2$. Treatment of Na$\sb2$Fe(CO)$\sb4$ with one equivalent of Ph$\sb2$BiCl in tetrahydrofuran affords Na$\lbrack\rm Ph\sb2BiFe(CO)\sb4\rbrack$, characterized as the (PPN) $\sp+$ salt. Adding a second equivalent of Ph$\sb2$BiCl to the same reaction produces (Ph$\sb2$Bi)$\sb2$Fe(CO)$\sb4$ or $\lbrack\rm PhBiFe(CO)\sb4\rbrack\sb2$, depending on the reaction time. (PhBiFe(CO)$\sb4\rbrack\sb2$ is also obtained in poor yield from the reaction of PhBiBr$\sb2$ and Na$\sb2$Fe(CO)$\sb4{\cdot}3/2$ dioxane in THF. (PhBiFe(CO)$\sb4\rbrack\sb2$, (PPN) (Ph$\sb2$BiFe(CO)$\sb4\rbrack$ and (Ph$\sb2$Bi)$\sb2$Fe(CO)$\sb4$ have been characterized by single crystal X-ray diffraction.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16427 |
| Date | January 1991 |
| Creators | Cassidy, Juanita Morgan |
| Contributors | Whitmire, Kenton H. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 393 p., application/pdf |
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