The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony

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.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Natural Sciences

Grantor

Rice University

Year dc:date.issued

1989

Author dc:creator

• Shieh, Minghuey

Advisor dc:contributor.advisor

• Whitmire, Kenton H.

• Inorganic chemistry

Statement dc:rights

• Copyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1911/16295

OAI identifier oai:identifier

oai:repository.rice.edu:1911/16295