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Complexes of rhenium and technetium with chelating thiourea ligands
Nguyen, Hung Huy

HaupttitelComplexes of rhenium and technetium with chelating thiourea ligands
TitelvarianteTechnetium- und Rheniumkomplexe mit chelatbildenden Thioharnstoffliganden
AutorNguyen, Hung Huy
Geburtsort: Hanoi, Vietnam
GutachterProf. Dr. Ulrich Abram
weitere GutachterProf. Dr. Konrad Seppelt
Freie SchlagwörterRhenium, Technetium, Thiourea, Complexes
DDC540 Chemie
ZusammenfassungThis thesis contains synthesis and structural characterization of novel technetium and rhenium complexes with chelating thiourea ligand systems, which include aroylthioureas and multidentate dialkylamino(thiocarbonyl)benzamidines.
N,N-Dialkylbenzoylthioureas (HR1R2btu) are versatile ligands and can stabilize rhenium and technetium in different oxidation states and/or with different cores. In all cases, they act as bidentate O,S-monoanionic ligands. Compositions and molecular structures of the products strongly depend on the precursors used and the reaction conditions applied.
The coordination behaviour of aroyl(bis-thiourea) ligands is similar to that of benzoylthioureas. In methanol and with the addition of a base such as Et3N, H2phth(R2tu)2, react with (NBu4)[ReOCl4] under formation of the dinuclear complexes [(ReO(OMe){phth(R1R2tu)2})2], which undergo dimerization via -oxo bridges to form the tetranuclear complexes [({ReOphth(R1R2tu)2}2O)2].
Various novel benzamidines, which can act as tri-, tetra- and pentadentate chelator systems, were successfully synthesized from N,N-dialkylamino(thiocarbonyl)benzimidoyl chlorides and functionalized amines.
The coordination chemistry of such ligand systems with rhenium and technetium is carefully studied. In most of the isolated complexes, the multidentate benzamidines coordinated to rhenium and technetium via S,N donor atoms of the original benzamidine skeleton and additional donor sites which are introduced into the molecule with the amine components.
The tridentate benzamidines prefer meridional coordination to rhenium(V) and technetium(V) oxo and nitrido cores and form stable complexes of the compositions [MOCl(L)] or [MN(L)(PPh3)] (M = Re, Tc). Some ongoing ligand exchange reactions of such complexes, giving access to ‘3 + 2’ mixed ligand complexes, were studied. A high level of cytoxicity was found for tridentate thiosemicarbazones and the corresponding [ReOCl(L)] complexes. Structure-Activity-Relationship studies of such compound were carried out by variation of substituted groups and/or the metal cores.
The tetradentate benzamidines are particularly suitable for rhenium(V) and technetium(V) oxo and nitrido cores. The structures of the complexes formed depend on the nature of the individual ligands and the charge compensation situation in the products, which finally leads to the formation of neutral complexes.
Pentadentate benzamidines were designed as chelator systems, which can fully wrap oxorhenium and oxotechnetium cores and form thermodynamically very stable complexes.
In order to apply the latter, potentially pentadentate ligands to biomolecule labelling, the bifunctional chelator H3L10-COOH was synthesized. Its oxorhenium(V) complex, [ReO(L10-COOH], was successfully labelled with a small peptide such as triglycine ethyl ester.
InhaltsverzeichnisTable of Content

Abbreviations xi
Abstract xiii
1 Introduction 1
2 Aroylthioureas and their Rhenium and Technetium
Complexes 3
2.1 Benzoylthioureas 3
2.1.1 Synthesis of N,N-Dialkyl-N’-benzoylthioureas and
Aroylbis(N,N-dialkyl-thioureas 3
2.1.1 Synthesis of N-Picolyl-N’-benzoylthiourea 4
2.2 Rhenium and Technetium Complexes with
Dialkylbenzoylthioureas. 5
2.2.1 ReVO and TcVO Complexes with Dialkylbenzoylthioureas 6
2.2.2 ReIII and TcIII Complexes with Dialkylbenzoylthioureas 16
2.2.3 ReV(NPh) Complexes with Dialkylbenzoylthioureas 19
2.3 A Rhenium Complex with N-Picolylbenzoylthiourea 22
2.4 Rhenium Complexes with Aroylbis(N,N-dialkylthioureas) 25
2.4.1 Rhenium Complexes with m-Phthaloylbis(N,N-dialkylthioureas) 25
2.4.2 A Rhenium Complex with
2,6-Dipicolinoylbis(N,N-diisobutylthioureas) 31
2.5 Summary and Conclusions 32
3 Benzamidines and their Rhenium and Technetium Complexes 33
3.1 Tridentate Benzamidines and their Rhenium and
Technetium Complexes 34
3.1.1 Tridentate N-(N’’,N’’-Dialkylaminothiocarbonyl)-N’-substituted
Benzamidines 34
3.1.1.1 Reactions of Benzimidoyl Chlorides with Function¬ali¬zed Primary
Amines 34
3.1.1.2 Reactions of Benzimidoyl Chlorides with Hydrazine Derivatives 36
3.1.2 Re and Tc Complexes with N’-(2-Hydroxyphenylbenzamidine
(H2L1) 39
3.1.2.1 ReVO and TcVO Complexes with H2L1 39
3.1.2.2 ‘3+2’ Mixed-Ligand Complexes of Re and Tc Containing H2L1 45
3.1.2.3 ReVN and TcVN Complexes with H2L1 56
3.1.3 A Rhenium Complex with N’-Picolylbenzamidine 57
3.1.4 A Rhenium Complex with N’-(2-Carboxyphenyl)benzamidine 59
3.1.5 Re and Tc Complexes with N’-(Benzamido)benzamidines (H2L4) 61
3.1.5.1 ReVO and TcVO Complexes with H2L4 61
3.1.5.2 ‘3+2’ Mixed-Ligand Complexes of Re Containing H2L4 63
3.1.6 Re and Tc Complexes with Benzamidines Derived from
4,4-Dialkylthiosemi-carbazide (H2L5) 65
3.1.6.1 ReVO and TcVO Complexes with H2L5 66
3.1.6.2 ReVN Complexes with H2L5 69
3.1.6.3 Biological Activity of Re Complexes with H2L5 71
3.1.7 Summary and Conclusions 74
3.2 Tetradentate Benzamidines and their Rhenium and Technetium
Complexes 75
3.2.1 Benzamidines Derived from o-Phenylenediamine (H2L6) and their Re
and Tc Complexes 76
3.2.1.1 Synthesis of H2L6 76
3.2.1.2 ReVO Complexes with H2L6 76
3.2.1.3 ReVN and TcVN Complexes with H2L6 80
3.2.2 Benzamidines Derived from o-Aminoacetophenon-4-methylthiosemicarbazone (H2L7) and their Re and Tc Complexes 82
3.2.2.1 Synthesis of H2L7 82
3.2.2.2 A ReVO Complex with H2L7 83
3.2.2.3 ReVN and TcVN Complexes with H2L7 85
3.2.3 Benzamidines Derived from o-Aminobenzylsalicylideneimine (H2L8)
and their Re and Tc Complexes 90
3.2.2.1 Synthesis of H2L8 90
3.2.2.2 A ReVO Complex with H2L8 93
3.2.2.3 A ReVN Complex with H2L8 94
3.2.4 Benzamidines Derived from a Triglycine Ester (H3L9) and
its Re Complex 96
3.2.4.1 Synthesis of H2L9 96
3.2.4.2 A ReVO Complex of H2L9 97
3.2.5 Summary and Conclusions 99
3.3 Rhenium and Technetium Complexes with Pentadentate
Benzamidines 101
3.3.1 Pentadentate N’-substituted Benzamidine 101
3.3.1.1 N’-{2-Methylene(phenyliminodiacetic)}benzamidine (H3L10) 101
3.3.1.2 N’-{Phenylene-(2-methyliminodiacetic)}benzamidine (H3L11) 102
3.3.2 ReVO and TcVO Complexes with H3L10 103
3.3.3 Rhenium Complexes with H3L11 106
3.3.3.1 ReVO Complexes with H3L11 106
3.3.3.2 ReV(NPh) Complexes with H3L11 108
3.3.4 Steps Toward Bioconjugation 111
3.3.4.1 Modification of H3L10 112
3.3.4.2 ReVO and TcVO Complexes with H3L10-COOEt and H3L10-COOH 113
3.3.4.3 Bioconjugation with a Small Peptide 117
3.3.5 Summary and Conclusions 118
4 Experimental Section 119
4.1 Starting Materials 119
4.2 Analytical Methods 119
4.3 Syntheses 120
4.4 Crystal Structure Determination 180
4.5 Biochemicals and Biological Studies 180
Summary 183
References 191
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SeitenzahlXIII, 200, 239 S.
Fachbereich/EinrichtungFB Biologie, Chemie, Pharmazie
Erscheinungsjahr2009
Dokumententyp/-SammlungenDissertation
Medientyp/FormatText
SpracheEnglisch
Rechte Nutzungsbedingungen
Tag der Disputation18.09.2009
Erstellt am21.09.2009 - 12:35:20
Letzte Änderung19.02.2010 - 13:59:28
 
Statische URLhttp://www.diss.fu-berlin.de/diss/receive/FUDISS_thesis_000000012877
URNurn:nbn:de:kobv:188-fudissthesis000000012877-6
Zugriffsstatistik
E-Mail-Adressehunghuy78@yahoo.com