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dc.contributor.advisor Whitmire, Kenton H.
dc.creatorShieh, Minghuey
dc.date.accessioned 2009-06-03T23:54:36Z
dc.date.available 2009-06-03T23:54:36Z
dc.date.issued 1989
dc.identifier.urihttps://hdl.handle.net/1911/16295
dc.description.abstract When (Et$\sb4$N) $\sb3$(Bi$\{$Fe(CO)$\sb4\}\sb4$) is treated with main group metal halides complicated disproportionation reactions occur. The reaction with BiCl$\sb3$ in MeCN yields (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{10}$), (Et$\sb4$N) $\sb2$(Bi$\sb2$Fe$\sb4$(CO)$\sb{13}$), and (Et$\sb4$N) $\sb2$(Bi$\sb4$Fe$\sb4$(CO)$\sb{13}$) while treatment with SnEt$\sb2$Cl$\sb2$ or CBr$\sb4$ gives the oxidation product (Et$\sb4$N) $\sb2$(Bi$\sb4$Fe$\sb4$(CO)$\sb{13}$) in high yield. Oxidation of (Et$\sb4$N) $\sb3$(Bi$\{$Fe(CO)$\sb4\}\sb4$) with 2 equivalents of (Cu(MeCN)$\sb4$) (BF$\sb4$) or MeI affords (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{10}$). (Et$\sb4$N) $\sb2$(Bi$\sb2$Fe$\sb4$(CO)$\sb{13}$) is oxidized by (Cu(MeCN)$\sb4$) (BF$\sb4$) forming Bi$\sb2$Fe$\sb3$(CO)$\sb9$ and reacts with CO (850 psi) to produce (Et$\sb4$N) $\sb2$(Bi$\sb4$Fe$\sb4$(CO)$\sb{13}$). Bi$\sb2$Fe$\sb3$(CO)$\sb9$ is reduced readily with Na/Hg forming one- and two-electron-reduction products. Two-electron-reduction can also be achieved by treating Bi$\sb2$Fe$\sb3$(CO)$\sb9$ with 2 equivalents of cobaltocene in CH$\sb2$Cl$\sb2$. The elemental analyses and spectroscopic data for the two-electron-reduction product support the formulation as (Cp$\sb2$Co) $\sb2$(Bi$\sb2$Fe$\sb3$(CO)$\sb9$). The (Bi$\sb2$Fe$\sb3$(CO)$\sb9$) $\sp{2-}$ anion can be reconverted to Bi$\sb2$Fe$\sb3$(CO)$\sb9$ in 90% spectroscopic yield when treated with (Cu(MeCN)$\sb4$) (BF$\sb4$). The reaction of (Et$\sb4$N) $\sb2$(Fe$\sb2$(CO)$\sb8$) with BiCl$\sb3$ or SbCl$\sb3$ forms compounds proposed to be (Et$\sb4$N) (EFe$\sb3$(CO)$\sb{12}$) (E = Bi, Sb) based on elemental analyses and spectroscopic data. The treatment of (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{12}$) or (Et$\sb4$N) (SbFe$\sb3$(CO)$\sb{12}$) with Cr(CO)$\sb5$(THF) produces (Et$\sb4$N) (EFe$\sb3$Cr(CO)$\sb{17}$) (E = Bi, Sb), respectively, while methylation of (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{12}$) afford Bi$\sb2$Fe$\sb2$(CO)$\sb8$Me$\sb2$. Oxidation of (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{12}$) with (Cu(MeCN)$\sb4$) (BF$\sb4$) yields Bi$\sb2$Fe$\sb3$(CO)$\sb9$ whereas the same reaction using of (Et$\sb4$N) (SbFe$\sb3$(CO)$\sb{12}$) gives Sb$\sb2$Fe$\sb6$(CO)$\sb{22}$. Refluxing (Et$\sb4$N) (BiFe$\sb3$(CO)$\sb{12}$) or (Et$\sb4$N) (SbFe$\sb3$(CO)$\sb{12}$) in acetonitrile produces (Et$\sb4$N) $\sb2$(Bi$\sb2$Fe$\sb4$(CO)$\sb{13}$) and (Et$\sb4$N) $\sb2$(Sb$\sb2$Fe$\sb5$(CO)$\sb{17}$), respectively. (Et$\sb4$N) (EFe$\sb3$Cr(CO)$\sb{17}$) (E = Bi, Sb), Bi$\sb2$Fe$\sb2$(CO)$\sb8$Me$\sb2$, (Et$\sb4$N) $\sb2$(Sb$\sb2$Fe$\sb5$(CO)$\sb{17}$), and Sb$\sb2$Fe$\sb6$(CO)$\sb{22}$ have been crystallographically characterized. (Et$\sb4$N) (EFe$\sb3$Cr(CO)$\sb{17}$) (E = Bi, Sb) displays a central main group atom bonded to one Fe$\sb2$(CO)$\sb8$ unit, one Cr(CO)$\sb5$ ligand, and one Fe(CO)$\sb4$ moiety. Bi$\sb2$Fe$\sb2$(CO)$\sb8$Me$\sb2$ contains a Bi$\sb2$Fe$\sb2$ parallelogram. A Me group is bonded to each pyramidal bismuth atom and the iron atoms are pseudooctahedrally coordinated. (Et$\sb4$N) $\sb2$(Sb$\sb2$Fe$\sb5$(CO)$\sb{17}$) has a square-planar Sb$\sb2$Fe$\sb3$ core geometry, with the external Fe(CO)$\sb4$ group bonded to each Sb atom. Sb$\sb2$Fe$\sb6$(CO)$\sb{22}$ is composed of an Fe$\sb2$(CO)$\sb6$ unit bridged by two Sb atoms. The coordination of each antimony atom is completed by bonding to an Fe$\sb2$(Co)$\sb8$ moiety.
dc.format.extent 151 p.
dc.format.mimetype application/pdf
dc.language.iso eng
dc.subjectInorganic chemistry
dc.title The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony
dc.type.genre Thesis
dc.type.material Text
thesis.degree.department Chemistry
thesis.degree.discipline Natural Sciences
thesis.degree.grantor Rice University
thesis.degree.level Doctoral
thesis.degree.name Doctor of Philosophy
dc.identifier.citation Shieh, Minghuey. "The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony." (1989) Diss., Rice University. https://hdl.handle.net/1911/16295.


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