Synthesis of Terminal Transition Metal Pnictide Complexes by Activation of Small Molecules

Abbenseth, Josh

dc.contributor.advisor	Schneider, Sven Prof. Dr.
dc.contributor.author	Abbenseth, Josh
dc.date.accessioned	2019-08-13T11:54:48Z
dc.date.available	2019-08-13T11:54:48Z
dc.date.issued	2019-08-13
dc.identifier.uri	http://hdl.handle.net/21.11130/00-1735-0000-0003-C18F-2
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-7599
dc.language.iso	eng	de
dc.publisher	Niedersächsische Staats- und Universitätsbibliothek Göttingen	de
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc	540	de
dc.title	Synthesis of Terminal Transition Metal Pnictide Complexes by Activation of Small Molecules	de
dc.type	doctoralThesis	de
dc.contributor.referee	Schneider, Sven Prof. Dr.
dc.date.examination	2019-07-08
dc.description.abstracteng	Coordination compounds involving metal-nitrogen bonds are a well-developed class of organometallic chemistry. In contrast, the chemistry of the heavier analogues of nitrogen, e.g. phosphorus and arsenic is far less explored. This thesis describes the synthesis and characterization of suitable rhenium and osmium PNP pincer compounds to serve as starting materials for further conversion towards heavy transition metal pnicogen complexes. A square-planar Os(II) PNP pincer complex is reported which features a unique electronic structure and serves as a convenient starting material to synthesize square-planar Os(IV) nitride complexes in unusual coordination spheres, as well as an open-shell phosphanyl radical complex. The conversion towards the corresponding phosphinidene complex is elucidated by calorimetric measurement and thermodynamical square-schemes. Furthermore, an unprecedented Os(IV) chloro-phosphinidene complex can be synthesized and its electronic structure is analyzed by quantum chemical calculations. In the case of rhenium, the synthesis of terminal phosphide and arsenide complexes is reported, enabled by linkage-isomerism of a coordinated pyrazol-pyridine ligand to allow for selective conversion. The electronic structure and reactivity of the terminal pnictide complexes is thoroughly analyzed. One-electron oxidation leads to pnicogen atom transfer to give donor-acceptor stabilized diphosphorus and diarsenic complexes which are characterized by QTAIM calculations. The terminal phosphide complex can be further converted towards low-molecular phosphorus oxide complexes by oxygen atom transfer. Finally, mechanistic aspects of dinitrogen splitting by molybdenum PNP pincer complexes are investigated by several spectroscopic techniques, including X-ray absorption spectroscopy.	de
dc.contributor.coReferee	Meyer, Franc Prof. Dr.
dc.contributor.thirdReferee	Wolf, Robert Prof. Dr.
dc.subject.eng	Coordination Chemistry	de
dc.subject.eng	Terminal Pnictide Complexes	de
dc.subject.eng	Proton-Coupled Electron Transfer	de
dc.subject.eng	Dinitrogen Splitting	de
dc.subject.eng	Phosphanyl Radicals	de
dc.subject.eng	Phosphinidenes	de
dc.subject.eng	Osmium Pincer Complexes	de
dc.subject.eng	Rhenium Pincer Complexes	de
dc.subject.eng	Molybdenum Pincer Complexes	de
dc.identifier.urn	urn:nbn:de:gbv:7-21.11130/00-1735-0000-0003-C18F-2-9
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.identifier.ppn	1672307384

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Fakultät für Chemie (inkl. GAUSS) [700]

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