<div class="csl-bib-body">
<div class="csl-entry">Glatz, M. (2018). <i>The role of sterics and electronics of PNP pincer ligands in Iron(II) and manganese(I) chemistry</i> [Dissertation, Technische Universität Wien]. reposiTUm. https://doi.org/10.34726/hss.2018.24302</div>
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dc.identifier.uri
https://doi.org/10.34726/hss.2018.24302
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dc.identifier.uri
http://hdl.handle.net/20.500.12708/6112
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dc.description
Abweichender Titel nach Übersetzung der Verfasserin/des Verfassers
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dc.description.abstract
Base metal catalysis is an emerging field in organometallic chemistry to replace precious metals by earth abundant metals. To achieve so, a suited ligand backbone to support the non-precious metals is needed, in order to get catalytic activity. The influence of well designed ligands on base metal chemistry is exampled on a series of iron(II) and manganese(II) compounds. The research bases on tridentate “pincer” ligands with a pyridine backbone connected with two phosphine donors (PNP-ligands). The ligands vary in the set-up of linkers (CH2, NH, NMe, O) and phosphine moiety PR2. A new class of iron(II) PNP pincer complexes, made up of two pincer ligands in different bonding modes (tridentate and bidentate) is described. The complexes of general formula κ3,κ2-[Fe(PNP)2X]+ are only observed when small phosphines (PR2; R = Me, Et, nPr, nBu, Ph) and a NH linker is apparent in the PNP ligands. In solution, the formation is inevitable, even when altering the stoichiometry. The 31P {1H} NMR gives rise to an A2B spin system for the coordinated phosphines, and a singlet for the vacant, non-coordinating phosphine. The X-ray structures reveal that a hydrogen bonding between NH linker and the pyridine nitrogen is stabilizing the coordination geometry. The distorted octahedral structure leads to a high degree of stress, which makes the bidentate ligand labile. Rearrangement to tridentate mode and displacement by carbon monoxide (CO) are possible. Carbonyl complexes of type [Fe(PNP)(CO)X2] are accessible, which are prone to CO release on thermal treatment, with increasing steric demand of the phosphine. Manganese(I) PNP pincer complexes of type [Mn(PNP)(CO)2H] were found to be pre-catalysts for the selective hydrogenation of aldehydes. Functional groups like ketones, nitriles, esters and olefins are tolerated. Among the selected PNP ligands, NH linkers delivered the best results. The results suggest that bifunctionality of the ligand along with ligand-metal cooperation is essential for the mechanism. Turnover numbers (TON) of up to 10.000 could be achieved. The hydrogenation proceeds at room temperature, without additives in protic media. Analogue rhenium(I) PNP pincer complexes [Re(PNP)(CO)2H] had inferior performance below 100 TON’s. Additionally, the hydrido complexes [Mn(PNP)(CO)2H] and [Re(PNP)(CO)2H] activate carbon dioxide (CO2) at ambient conditions. The 1,2-addition of CO2 leads to a series of formate complexes of the types [Mn(PNP)(CO)2(OCHO)] and [Re(PNP)(CO)2(OCHO)]. In summary, these results offer a guide for Mn(I) and Fe(II) pincer chemistry allowing to alter the chemical properties in a modular fashion.
en
dc.language
English
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dc.language.iso
en
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dc.rights.uri
http://rightsstatements.org/vocab/InC/1.0/
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dc.subject
Pincer Ligands
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dc.subject
Pincer Complexes
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dc.subject
Base Metals
en
dc.subject
Iron
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dc.subject
Manganese
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dc.title
The role of sterics and electronics of PNP pincer ligands in Iron(II) and manganese(I) chemistry
en
dc.title.alternative
Sterische und elektronische Einflüsse auf PNP Pincer Liganden in der Eisen(II) und Mangan(I) Chemie
de
dc.type
Thesis
en
dc.type
Hochschulschrift
de
dc.rights.license
In Copyright
en
dc.rights.license
Urheberrechtsschutz
de
dc.identifier.doi
10.34726/hss.2018.24302
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dc.contributor.affiliation
TU Wien, Österreich
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dc.rights.holder
Mathias Glatz
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dc.publisher.place
Wien
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tuw.version
vor
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tuw.thesisinformation
Technische Universität Wien
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tuw.publication.orgunit
E163 - Institut für Angewandte Synthesechemie
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dc.type.qualificationlevel
Doctoral
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dc.identifier.libraryid
AC15022052
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dc.description.numberOfPages
105
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dc.identifier.urn
urn:nbn:at:at-ubtuw:1-110717
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dc.thesistype
Dissertation
de
dc.thesistype
Dissertation
en
dc.rights.identifier
In Copyright
en
dc.rights.identifier
Urheberrechtsschutz
de
tuw.advisor.staffStatus
staff
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tuw.advisor.orcid
0000-0003-0872-6159
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item.fulltext
with Fulltext
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item.cerifentitytype
Publications
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item.mimetype
application/pdf
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item.openairecristype
http://purl.org/coar/resource_type/c_db06
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item.languageiso639-1
en
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item.openaccessfulltext
Open Access
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item.openairetype
doctoral thesis
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item.grantfulltext
open
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crisitem.author.dept
E163-01-1 - Forschungsgruppe Organometallische Chemie und Katalyse