{"id":{"repo_id":"rice","oai_identifier":"oai:repository.rice.edu:1911/16295"},"canonical_url":"https://search.dev.ndltd.org/etd/rice/oai:repository.rice.edu:1911/16295","repository":{"repo_id":"rice","name":"Rice University","base_url":"https://repository.rice.edu/server/oai/request"},"display":{"title":"The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony","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.","abstract_html":"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.","abstract_has_math":true,"creators":["Shieh, Minghuey"],"institution":"Rice University","degree_name":"Doctor of Philosophy","degree_level":"Doctoral","degree_discipline":"Natural Sciences","degree_department":null,"school":null,"contributors":[],"advisors":["Whitmire, Kenton H."],"committee_chairs":[],"committee_members":[],"year":1989,"date_issued":"1989","date_published":"1989","updated_at":"2026-07-24T04:10:30Z","subjects":["Inorganic chemistry"],"languages":["eng"],"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."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1911/16295","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Whitmire, Kenton H."]},{"key":"dc:creator","label":"Author","values":["Shieh, Minghuey"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2009-06-03T23:54:36Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2009-06-03T23:54:36Z"]},{"key":"dc:date.issued","label":"Date","values":["1989"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Natural Sciences"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Rice University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Inorganic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["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."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1911/16295"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony"]}]}],"canonical_facts":{"dc:contributor.advisor":["Whitmire, Kenton H."],"dc:creator":["Shieh, Minghuey"],"dc:date.accessioned":["2009-06-03T23:54:36Z"],"dc:date.available":["2009-06-03T23:54:36Z"],"dc:date.issued":["1989"],"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.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/1911/16295"],"dc:language.iso":["eng"],"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."],"dc:subject":["Inorganic chemistry"],"dc:title":["The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony"],"dc:type":["Thesis"],"thesis:degree_discipline":["Natural Sciences"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["Rice University"]},"updated_at":"2026-07-24T04:10:30Z"}