|
Identifier |
000438522 |
Title |
Σύνθεση, χαρακτηρισμός και μελέτη σύμπλοκων ενώσεων του Ρηνίου |
Alternative Title |
Synthesis, characterization and study of Rhenium complexes |
Author
|
Καλοφωλιάς, Δημήτρης
|
Thesis advisor
|
Μήλιος, Κωνσταντίνος
|
Reviewer
|
Δημάδης, Κωνσταντίνος
Τρικαλίτης, Παντελής
Κουτσολέλος, Αθανάσιος
Σπύρος, Απόστολος
Αρματάς, Γεράσιμος
Παπαευσταθίου, Ιωάννης
|
Abstract |
Employment of 2-hydroxy-naphthaldehde (naphtH), 2-(β-naphthalideneamino)-2- hydroxymethyl-1-propanol (H3L) and 2-amino-isobutyric acid (aibH) in rhenium chemistry has led to the isolation of thirteen new Re complexes with the metallic centre found at the +1, +3, +4, +5 and +7 oxidation states:
1. trans-[ReIIICl2 (napht)(PPh3)2]
2. trans-[ReIIICl2 (C11H7O)(PPh3)2]
3. [ReVIIO4] . [OHC10H6CH2PPh3] . EtOH
4. [ReIII2Cl4 (HL)(PPh3)]. 2C7H8
5. [ReIVCl2 (HL)(PPh3)]
6. [ReIV/V4O4Cl8] . Cl. DMF. 2HN(CH3) 2
7. [ReV OCl2 (aib)(PPh3)]
8. [ReV OCl(aib) 2]
9. [ReIII2 (OΗ)Cl3 (aib) 2 (PPh3) 2] . C7H8 . EtOH
10. [ReIV2OCl4 (aib) 2 (PPh3) 2]
11. cis-[ReIII2Cl4 (Haib) 2 (DMF) 2] . 2Cl. 3DMF
12. [ReV Cl2 (aib)(PPh3)(NCH(CH3) 2)]
13. trans-[ReI Cl(CO) 2 (DMF)(PPh3) 2] . DMF
The isolated products were structurally characterized by Single Crystal X-Ray Crystallography and further investigated by means of Nuclear Magnetic Resonance – NMR (complexes 7, 8, 11. 2Cl. 3DMF and 12) and Ultra Violet-Visible – UV-Vis (complexes 1, 4. 2C7H8, 5, 7, 8, 9. C7H8 . EtOH, 11. 2Cl. 3DMF and 12) spectroscopy. In addition, dc magnetic susceptibility and various field/ temperature magnetization measurements have been performed in order to investigate the magnetic properties of 1, 4. 2C7H8, 5 and 9. C7H8 . EtOH. Furthermore, DFT calculations were carried out in order to elucidate the structural and electronic properties of compounds 1, 4. 2C7H8, 5 and 11. 2Cl. 3DMF.
Among these results, this Thesis reports on the first example of a dinuclear rhenium complex with a triple metal-metal bond between Re(III) centers, complex [ReIII2Cl4 (HL)(PPh3)]. 2 C7H8 (4. 2 C7H8), almost 55 years since the discovery of multiple metallic bonds in coordination compounds.
Finally, the synthesis and structural characterization of three new compounds, [ReVOCl(ala) 2] (14), [H2O(OPPh3)4MnIIOReVIIO3] . [ReVIIO4] (15) and [Mn7II (CH3CH2CH2O) 12] . 2[ReVIIO4] (16) are reported, as the initial results of Re/ alanine and mixed metal Re-Mn/ H3L systems.
|
Language |
Greek |
Subject |
Bonds |
|
Coordination complexes |
|
Crystallographic structures |
|
Magnetic properties |
|
Metallic bond |
|
Molecular magnetism |
|
Multiple metal-metal |
|
NMR spectroscopy |
|
Single X-RAY crystallography |
|
Single molecular magnets |
|
Theoretical calculations DFT |
|
UV-VIS spectroscopy |
|
Ενώσεις συναρμογής |
|
Θεωρητικοί υπολογισμοί DFT |
|
Κρυσταλλογραφική δομή |
|
Μαγνήτες μοναδικού μορίου |
|
Μαγνητικές ιδιότητες |
|
Μεταλλικός δεσμός |
|
Μοριακός μαγνητισμός |
|
Πολλαπλοί δεσμοί μετάλλου-μετάλλου |
|
Ρήνιο |
|
Σύμπλοκα |
|
Σύμπλοκες ενώσεις |
|
Φασματοσκοπία NMR |
|
Φασματοσκοπία UV-VIS |
Issue date |
2019. |
Collection
|
School/Department--School of Sciences and Engineering--Department of Chemistry--Doctoral theses
|
|
Type of Work--Doctoral theses
|
Permanent Link |
https://elocus.lib.uoc.gr//dlib/0/9/a/metadata-dlib-1616409839-766215-30368.tkl
|
Views |
168 |