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1
Blagg, Robin Joseph. « Rhodium(I) complexes of sulfur-donor scorpionate ligands ». Thesis, University of Bristol, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.446152.
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Lopez-Gomez, Maria J. « Scorpionate, boratrane and related complexes of rhodium and iridium ». Thesis, University of Bristol, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.508124.
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Frazer, Andrew. « Synthesis and characterisation of indium complexes with scorpionate ligands ». Thesis, University of Hertfordshire, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358306.
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Liang, Shengwen. « Nitrene Transfer Reactions Mediated by Transition Metal Scorpionate Complexes ». Ohio University / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1339005115.
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Bell, Nicola Louise. « Bridgehead substituted scorpionates providing helically chiral complexes ». Thesis, University of Edinburgh, 2013. http://hdl.handle.net/1842/7949.
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Tripodal borate ligands, including Tp and Tm, are some of the most widely used in organometallic chemistry and were originally prepared, as anions, from the reaction of the relevant heterocycle with an alkali metal borohydride. However, an alternate route, allowing access to zwitterionic, charge-neutral, scorpionates was recently developed within the Bailey group using tris(dimethylamino)borane as the boron source. This thesis describes the expansion of the borane synthetic route to create new, charge-neutral, zwitterionic, tris(methimazolyl)borate (ZTm) ligands containing B-N, B-O and B-C coordinate bonds. Unusual reactivity with isonitrile donors is also presented which has allowed access to boron substituted anionic Tm ligands from the charge-neutral starting material, (HNMe2)ZTm. Attempts to control the helical chirality of ZTm complexes, by using chiral imidazoline donors on the central boron are also described. The borane synthetic route has allowed access to the novel ligand ZThp, the first example of a tripod based on 2-hydroxypyridine ligand arms. As with Tm, this ligand exhibits helical chirality upon complexation and demonstrates how individual atom hybridisation within the ligand arms affects the helicity and thus the chirality of flexible scorpionate ligands. Coordination studies of both zwitterionic and boron-substituted anionic Tm ligands have shown a tendency for the formation of ‘sandwich’ complexes of the form L2M with some metal precursors, whilst the formation of the corresponding ‘half-sandwich’ complexes of these ligands with ruthenium and rhodium was found to be disfavoured.
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Hamilton, Alexander J. « Structural and Computational Investigations into Phosphine and Scorpionate Ligand Complexes ». Thesis, University of Bristol, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.525458.
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PAPINI, Grazia. « New metal complexes supported by scorpionate and macrocyclic ligands : chemistry and biological studies ». Doctoral thesis, Università degli Studi di Camerino, 2008. http://hdl.handle.net/11581/401890.
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I and my research group have focused our attention on the study of the coordinative ability of monoanionic heteroscorpionate ligands based on bis(pyrazol-1-yl)methanes containing acetate or sulfonate groups as the third coordinating moiety in particular toward rhenium. The similarity between technetium and rhenium chemistry, in fact, determined a widespread use of the latter as a technetium surrogate to perform macroscopic chemistry of potential radiopharmaceuticals. In this way, a ‘‘cold'' material (the natural isotopic mixture of 185Re and 187Re) can be advantageously manipulated instead of the radioactive nuclide 99gTc (t1/2 = 2.12 105 y, Ea'¢ = 292 keV). On the other hand, rhenium has two a'¢- emitters isotopes 186Re (a'¢-max = 1.07 max = 2.10 MeV; t1/2 = 17 h) which are of great interest to nuclear medicine due to their physical and nuclear properties finalized to a potential application in the radiopharmaceutical. For this reason, a renewed interest in rhenium coordination chemistry fluourished, finalized to a potential application in the radiopharmaceutical field of rhenium itself, which was no longer considered as a mere technetium substitute for chemical investigations at macroscopic level. In the past few years the so-called ‘‘metal fragment'' strategy for the synthesis of new technetium and rhenium radiopharmaceuticals revealed to be a promising approach. This methodology is based on the preparation of intermediate species comprising a stable building- block constituted by the metal and suitable ancillary ligands and labile modentate groups (e.g., water molecules or halide groups), which can be easily replaced by chelating bi- or tri-dentate ligands eventually conjugated to a specific biomolecule. According to this strategy, we have reported on a new class of compounds containing the stable metal fragment [Re(O)(NNO)]2+ (N,N,O = tripodal heteroscorpionate ligand). In fact, in order to stabilize the monooxo rhenium core, heteroscorpionate ligands were chosen due to their coordinative flexibility and proper (facial) stereochemical arrangement. In particular, monoanionic bis(pyrazol-1-yl)methane derivatives, containing acetate (Hbpza = bis(pyrazol-1-yl)acetate; Libdmpza = Lithium[Bis(3,5-dimethylpyrazol-1-yl)acetate]) or sulfonate groups (Libdmpzs = Lithium[Bis(3,5-dimethylpyrazol-1-yl)methanesulfonate]), by reaction with [NBu4][Re(O)Cl4], gave a series of intermediate compounds Re(O)(NNO)Cl(X), where the octahedral coordination sphere is filled with two modentate groups (X = Cl or OR) whose structure depends on the type of NNO ligand and solvent utilized. Besides, we have seen that the effectiveness of replacement of two modentate groups of intermediate species with a bidentate chelate (ethylene glycol, malonic acid and 1,3-propandiol) depends on the nature of the heteroscorpionate, and that the substitution takes place easily when N,N,O ligand bear methylated pyrazolyl rings
8
Doyle, Garry Anthony. « The syntheses and characterisation of some halogenonitrosyl hydrotris(3,5-dimethylpyrazol-1-yl)borato complexes of molybdenum ». Thesis, University of Bristol, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.313082.
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Meinholz, Margret [Verfasser], Dietmar [Akademischer Betreuer] Stalke, Franc [Akademischer Betreuer] Meyer et Lutz [Akademischer Betreuer] Ackermann. « Metal complexes of Scorpionate-Like Polyimido Sulphur Phosphanyl Ligands / Margret Meinholz. Gutachter : Dietmar Stalke ; Franc Meyer ; Lutz Ackermann. Betreuer : Dietmar Stalke ». Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2011. http://d-nb.info/1043992413/34.
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Aboelenen, Ahmed. « Development of 3d Transition Metal Complexes of Hydrotris(pyrazolyl)borates (Tp) asRedox Catalysts ». Ohio University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1572809656086338.
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James, Christopher Dominic. « PARAMAGNETIC RESONANCE STUDIES OF HIGH-SPIN COBALT (II) COORDINATION COMPLEXES ». Miami University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=miami152267342524459.
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Vives, Guillaume. « Synthèse d'une famille de moteurs moléculaires rotatifs ». Toulouse 3, 2007. http://www.theses.fr/2007TOU30088.
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Une famille de moteurs moléculaires rotatifs a été synthétisée en vue de leur étude au niveau de la molécule unique par microscopie en champ proche. Le moteur est basé sur un complexe de ruthénium de géométrie en tabouret de piano avec deux ligands constituant un rotor et un stator. Le stator est un ligand tripodal hydrotris(indazolyl)borate fonctionnalisé pour s'accrocher à la surface d'étude. Le rotor est un ligand cyclopentadiényle (Cp) connecté à cinq groupements électroactifs ferrocényles via des espaceurs rigides et linéaires. Le moteur sera déposé entre deux électrodes d'une nanojonction afin de contrôler la rotation par le passage d'un courant. Deux ligands hydrotris(indazolyl)borate fonctionnalisés par des groupements ester ou thio-éther ont été synthétisés afin de permettre un accrochage du moteur respectivement sur des surfaces d'oxydes ou métalliques. Ces ligands ont été incorporés à une première génération de moteurs où les ferrocényles sont connectés par un lien conjugué au Cp central. L'utilisation de fragment isolant trans-platine ou biyclo[2,2,2]octane entre les groupements électroactifs a été étudiée afin de minimiser les transferts d'électrons intramoléculaires. Une étude expérimentale et une étude théorique a montré la diminution du paramètre de couplage électronique, par rapport à un lien conjugué d'un facteur trois avec un fragment trans-platine et d'un ordre de grandeur avec un bicyclo[2,2,2]octane. Ces espaceurs isolants ont ainsi été introduits dans les bras du rotor pour conduire à des moteurs moléculaires totalement fonctionnels. Afin de mettre en évidence la rotation, des moteurs ayant un rotor dissymétrique ont été également été synthétisésA family of electrically fuelled rotary molecular motors has been synthesised to be studied by near field microscopy at the level of a single molecule. The motor is based on a ruthenium complex with a piano stool geometry bearing two different ligands that act as a rotor and a stator. The stator is a tripodal hydrotris(indazolyl)borate ligand functionalized to interact strongly with the surface. The rotor is a cyclopentadienyl (Cp) ligand connected to five electroactive groups (ferrocene) by linear and rigid arms. The motor will be deposited between two electrodes of a nanojonction to control the rotation by a flow of current. Two hydrotris(indazolyl)borate ligands functionalised with ester or thio-ether groups have been synthesised to anchor the motor respectively to an oxide or to a metallic surface. These ligands have been incorporated into a first generation of motors where the ferrocenes are connected by a conjugated linker to the central Cp. .
13
Günyar, Alev Topaloğlu Sözüer Işıl. « Oxo-Imido molybdenum tripyrazolyl borate complexes/ ». [s.l.] : [s.n.], 2004. http://library.iyte.edu.tr/tezler/master/kimya/T000464.pdf.
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Ghana, Priyabrata [Verfasser]. « Synthesis, Characterization and Reactivity of Ylidyne and µ-Ylido Complexes Supported by Scorpionato Ligands / Priyabrata Ghana ». Bonn : Universitäts- und Landesbibliothek Bonn, 2018. http://d-nb.info/1180495381/34.
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ORBISAGLIA, SERENA. « From pyrazole- to imidazole-based N-donor Ligands : Coordination Chemistry and Applications of New Late Transition Metals Complexes with Scorpionates, Poly(pyrazolyl)alkanes and NHCs ». Doctoral thesis, Università degli Studi di Camerino, 2014. http://hdl.handle.net/11581/401839.
Texte intégralRésumé :
The nature of ligands coordinated to the metal ion mostly determines the properties of the inorganic, organometallic or bioinorganic model compounds. The pyrazole is one of the most studied heterocyclic aromatic compounds in coordination chemistry as single ligand or incorporated in polidentate ligands, such as in poly(pyrazolyl)borates (‘scorpionates'), poly(pyrazolyl)alkanes, etc. The great versatility of the pyrazole allows the formation of several ligands with different functionalizations, which mainly influence the geometry and nuclearity of the diverse coordination complexes afforded by the reaction of the pyrazole-based chelating ligands and a metal ion. Another of the most studied heterocyclic aromatic compounds in coordination chemistry is an analogue of pyrazole with two non-adjacent nitrogen atoms, the imidazole, which represents the main structure of the most common and studied N-Heterocyclic carbenes (NHCs), in particular the imidazolâ€2â€ylidenes. These general informations arouse curiosity in main features and reactivity, synthesis and coordination modes, potential and ensured applications of various N-donor ligands, such as poly(pyrazolyl)borates or scorpionates, their isoelectronic and isosteric neutral analogues poly(pyrazolyl)alkanes and N-heterocyclic carbenes, presented, thus, in detail, in Chapter 1. The focus on the electronic and steric properties, the coordinating behaviour and several applications of scorpionates metal complexes, the state-of-art on coordination chemistry and reactivity of the poly(pyrazolyl)alkanes derivatives, the advantages of NHCs over phosphines, including ease of handling, minimal toxicity and powerful electron-donating properties, as enhanced stability of their transition metal complexes, which lead to the synthesis of highly active derivatives in homogeneous catalysis, anticipate the research work of this thesis on the nitrogen pyrazole- and imidazole-based ligands and their organometallic compounds. Beginning from Chapter 2, which describes the aims of the research work, all the chapters are divided in four sub-chapters. In the first sub-chapter differently halogen substituted bis- and tris-(pyrazolyl)borate ligands (BpBr3, TpBr3 and TpiPr,4Br) are compared in terms of electron-donor character through their interactions with various ruthenium(II) arene dimers, as also through electrochemical studies. Interestingly, an unexpected dinuclear ionic compound accounted for by its low thermodynamic stability, confirmed by theoretical calculations at the DFT level, due to steric reasons. The second sub-chapter is centered on the synthesis, characterization and crystal structure of the complexes of the second-lowest steric hindrance scorpionate ligand, TpTn, towards CuI, CuII, ZnII and CdII acceptors. A remarkable coordinative aspect of this ligand is pointed out, as well as the thermal and air stability of the relative complexes, confirmed by thermogravimetric and differential thermal analysis (TGA-DTA). By contrast, the interaction between TpTn and PtI2 proceeded through ligand decomposition, affording a monomeric complex. In the third sub-chapter, the varying, different stoichiometries and the N,N-chelating coordination modes of the bis(pyrazolyl)methanes, in particular of the two indazolyl-based regio-isomeric ligands, L1, bis(1H-indazol-1-yl)methane, and L2, bis(2H-indazol-2-yl)methane, toward XI group metal centers are studied. The synthesis and full characterization of analogous adducts of both regio-isomers allow a systematic comparison of their structural and spectral features, depending on the regio-isomeric ligand and counter-ion used, and the reaction conditions employed. The synthesis and characterization of a new series of stable, cationic gold(I/III) NHC complexes, as well as their catalytic activity in five well-established organic gold-mediated transformations, performed at the University of Strasbourg, under guidance of Director of Research Pierre Braunstein and coworkers (Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Universita'© de Strasbourg, France) is described in the fourth sub-chapter. Interestingly, various attempts to synthesize gold(III) NHC bis- or tris-pyridine complexes, as also the comparative behaviour of NHCs respect to phosphine ligands, are presented. Going further on the thesis structure, all the general procedures and experimental data are reported in Chapter 3, while the discussion and elaboration of the results are described in Chapter 4. Concluding remarks and future perspectives are discussed in Chapter 5, whereas all the references and some notes are given in Chapter 6. In Annexes section, the Curriculum Vitae, the List of Pubblications and the Contributions to Congresses are presented.
16
Türkoglu, Gazi [Verfasser]. « Scorpionate complexes for copolymerization and molecular imprinting / Gazi Türkoglu ». 2011. http://d-nb.info/1011413183/34.
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Meinholz, Margret. « METAL COMPLEXES OF SCORPIONATE-LIKE POLYIMIDO SULPHUR PHOSPHANYL LIGANDS ». Doctoral thesis, 2011. http://hdl.handle.net/11858/00-1735-0000-0006-B069-D.
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朱紹翔. « Copper Complexes of Monoanionic N,N,S-Scorpionate Ligand：Model Study of 2-His-1-Cys Non-Heme Metalloproteins and Silver Complexes of Monoanionic N,N,O-Scorpionate Ligand ». Thesis, 2007. http://ndltd.ncl.edu.tw/handle/31643477245914124044.
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碩士國立彰化師範大學
化學系
95
In order to mimic the function and active site structure of copper proteins such as：nitrite reductase, nitrous oxide reductase, amine oxidase, dopamine ß-monooxygenase and peptidylglycine α-hydroxylating monooxygenase, the N2S scorpionate ligand with methyl as substituents [{Li(bdmpzdta)(H2O)}4] (bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate) and with t-butyl as substituents bdtbpzdta have been synthesized. Three copper complexes , Cu(Ⅱ)(bdmpzdta)2 (1), [Cu(Ⅰ)(bdtbpzdta)Br]2 (2) and {Cu(Ⅰ)2[µ-S-(bdtbpzdta)2]}2 (3) have been obtained . During the characterization of copper complexes we found an exchange reaction that the dithioacetate moiety has been slowly converted to acetate group in the presence of carbon dioxide. There is no precedent example on the C-C bond cleavage in either [{Li(bdmpzdta)(H2O)}4] or mental complex of N2S ligand . Our observation represents an unique example of CC bond activation promoted by metal ion and, more importantly, this type of compound might be able to carry out the CO2 fixation reaction. In the second part of research, multidentate N2O ligands are used to bridge metal centers to form clusters or polymeric structures via coordination bonds. The N2O scorpionate ligand bdmpza (= bis(3,5-dimethylpyrazol-1-yl) has been used because carboxylate group can bridge to metal centers. The silver complexes, K4{[Ag(bdmpza)2]2}(ClO4)2(Acetone)2 (4), [Ag4(bdmpza)3]2(OH)(ClO4) (5), and ({Na[Ag(bdmpza)]2BF4(H2O)}2)n (6) have been synthesized and structure characterized. These silver complexes demonstrate the importance of cation and anion on controlling the three dimensional structure. In the case of complex (6) linear chain structure forms. It is optimistic that other two dimensional or three dimensional supramolecular structures can be constructed using this type of N2O coordinating ligand.
19
Fianchini, Mauro. « Scorpionate supported and unsupported carbonyl and ethylene complexes of group 11 metals / ». 2009. http://hdl.handle.net/10106/2059.
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Squillantini, Lorenzo. « Spin Crossover complexes : from synthesis to surface assembly ». Doctoral thesis, 2021. http://hdl.handle.net/2158/1235501.
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In this thesis various spin crossover complexes have been synthesized and nanostructured using various techniques. Thermal high vacuum sublimation and chemisorption through hydrosilylation have been used to fabricate the nanomaterials. Characterization of the obtained nanostructures has been performed by using surface-sensitive spectroscopic techniques (XPS and XAS). Furthermore, a spin crossover-based nanomaterial has been integrated in a nanojunction.
21
Roy, Sovan. « Photocytotoxicity And DNA Cleavage Activity Of Metal Scorpionates And Terpyridine Complexes ». Thesis, 2010. http://etd.iisc.ernet.in/handle/2005/1376.
Texte intégralRésumé :
Scorpionate and terpyridine ligands are of importance in inorganic chemistry for their metal-binding properties. Tris-pyrazolylborate (Scorpionate) ligands that show facial binding mode and steric protection have been extensively used to synthesize complexes modeling the active site structure and biological function of various metalloproteins and as catalysts in C-H and NO activation and carbine transfer reactions. Terpyridine and modified terpyridine ligands showing meridional binding mode have been used in bioinorganic chemistry where Pt-terpyridine complexes are known to inhibit the activity of thiordoxin reductase (TrxR) besides showing interaction with G-quadruplex. The thesis work stems from our interest to use these ligand systems to design and prepare new 3-d metal-based photodynamic therapeutic (PDT) agents to explore their visible light-induced DNA cleavage activity and photocytotoxicity. Efforts have been made in this thesis work to design and synthesize Co(II) and Cu(II) complexes having scorpionate (Tpph) abd terpyridine (tpy) ligands.
Ternary 3d-metal complexes having Tpph and planar phenanthroline bases have been synthesized and structurally characterized. The steric encumbrance of Tpph has led to the reduction in chemical nuclease activity along with enhanced photo-induced DNA cleavage activity, particularly of the Cu(II) and Co(II) complexes. The Co(II), Cu(II) and Zn(II) complexes of Tpph and a pyridyl ligand having a photoactive naphthalilmide moiety show molecular light-switch effect on binding to calf thymus DNA or BSA protein. The complexes do not show any chemical nuclease activity. The Cu(II) complex shows significant DNA cleavage activity in red light. The Co(II) complex displays significant photocytotoxicity in UV-A light. Ternary Cu(II) complexes of ph-tpy and heterocycylic bases are prepared and their DNA binding and cleavage activity studied. The complexes are avid binders to CT-DNA. The dipyridoquinoxaline (dpq) and dipyridophenazine (dppz) complexes are photocleavers of DNA in visible light. A significant enhancement in cytotoxicity in HeLa cancer cells is observed on exposure of the dppz complex to light. The binary Cu(II) complexes are also prepared to reduce the dark toxicity using phenyl and pyrenyl substituted terpyridine ligands. The pyrenyl substituted complex shows DNA cleavage activity in the visible light, low dark toxicity and unprecedented photocytotoxicity in visible light. The copper(II) complexes generally show dark cellular toxicity due to the presence of reducing thiols. The present terpyridine copper(II) complex having pendant pyrenyl moiety shows significant PDT effect that is similar to that of the PDT drug Photofrin. Binary Co(II) complexes show efficient DNA cleavage activity in visible light, significant photocytotoxicity in visible light and cytosolic uptake behaviour. Considering the bio-essential nature of the cobalt and copper ions, the present study opens up new strategies for designing and developing 3d-metal-based photosensitizers for their potential applications in PDT.
22
Li, Jia-shan, et 李佳珊. « Synthesis and Characterization of Copper N,N,O-Scorpionate Complexes and Study of C−H Activation ». Thesis, 2014. http://ndltd.ncl.edu.tw/handle/29848581014361539181.
Texte intégralRésumé :
碩士國立中央大學
化學學系
102
In order to mimic the active site structure and function of copper proteins, the N,N,O-hetroscorpionate ligand, Lithium 2,2-bis(3,5-di-tert-butylpyrazol-1-yl)acetate (3) has been synthesized. Pyrazole rings of ligand were used to mimic imidazole of histidine. A sterically constrained group like tert-butyl group is added to each pyrazole rings that in order to mimic the bulky protein peptide chains. Treatment of ligand Li(bdtbpza) (3) with divalent cupric salt, Cu(NO3)2．2.5H2O, resulted in the formation of two complexes [CuII(bdtbpza)(NO3)] (4) and [CuII2(bdtbpza)2(NO3)2] (5). The conversion between complexes (4) and (5) is temperature-dependent. Complex (4) was achieved at ambient temperature while complex (5) was obtained at low temperature (< −20 oC). The reaction of complex (4) and zinc amalgam in different solvents led to different structures i.e. [ZnII2(bdtbpza)2(NO3)2] (6) from DMF and [CuI3(bdtbpza)3ZnII(NO3)2] (7) from THF. On the other hand, copper(I) complex [CuI3Li(bdtbpza)3(MeOH)](PF6) (8) was synthesized by using [Cu(CH3CN)4](PF6) as the starting metal source. To study copper oxygenases, reduction of complex (4) or (5) and further conducting with O2(g) process C−H activation and oxygenation to [Cu2II(bdtbpzaO)2] (9), which was also got from a reaction of CuI-containing complex (7) or (8) with O2(g). Interestingly, the reaction of complex (8) and O2(g) not only achieved the dimeric product, (9), but isolated another monomeric product, [CuII(bdtbpzaOH)(DMF)](PF6) (10) was. The activation process is monitored by UV-Vis spectra and ESI-Mass spectra. In the activation of complex (4) at ambient temperature, the time-course UV-Vis showed the absorbance of d−d transition increasing with lengthening time, and the wavelength shifted to higher energy gradually. In the time-course UVVis spectra at −55 oC, the activation of complex (8) exhibited an increasing intensity of the absorption band at 357 and 659 nm. This absorption spectrum was similar to that of complex (9); therefore, it cannot be absolutely assigned as the result from neat CuII−superoxide, CuII−peroxide, complex (9) or (10). In the experiment of tracking ESI-Mass, the fragement, m/z = 599.3, was considered to be copper(II)peroxide. The demetallation of the product (9) from CH activation gave a new ligand, [Na2(bdtbpzaO)2] (11), which allows us to extent another new model chemistry.
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Tsai, Kuang, et 蔡光. « N,N,O-Scorpionate Metal Complexes as Model Compounds : Mn for SOD and Cu for Oxygenase Mimic ». Thesis, 2005. http://ndltd.ncl.edu.tw/handle/68688383033687692342.
Texte intégralRésumé :
碩士國立彰化師範大學
化學系
93
Abstract In order to mimic the function and active site structure of manganese and copper proteins, the N,N,O scorpionate ligand Libdtbpza．H2O (lithium 2,2-bis(3,5-di-tert-butyl-1H-pyrazol-1- yl)acetate monohydrate) has been synthesized. Pyrazole rings were used to mimic histidine and carboxylate group presence in aspartate or glutamate. In order to mimic the bulky protein peptide chains, we add tert-butyl group, a stereo constrained group, to each pyrazole rings. A series of manganese(II) complexes, {[Li(bdtbpza)]3Mn(H2O)2 (ClO4)}+ClO4- (1) (monomer), [Li(bdtbpza)]3Mn(H2O)(µ-Br)2 MnBr2 (2) (dimer) and a unusual trinuclear manganese complex (bdtbpza)6Na6Mn6(OAc)6(H2O)6 (3) have beed synthesized. The electronic states, magnetic properties of complexe (1) and (2) are studied by means of EPR spectra, and SQUID magnetic susceptibilities measurements. The redox properties of complex(1) and (2) are studied by means of Cyclic Voltammetry and are compared with MnSOD. The structures and coordination environments of complexs (1)~(3) are characterized and studied by X-ray single crystal differactometer. For Oxygenases, we controlled the time of bubbling O2 to increase the yield of [Cu(bdtbpzaO)]2 (5) which is the oxygenation product of intermediate complex (4a), a reduced compound of [Cu(bdtbpza)(NO3)]2 (4) . In order to suggest a mechanism for oxygenation , we carried out isotope labelling study and detect it by means of LCMS.We find that some agostic interaction between Cu and C-H bond in complex(5)，when we reduced it from Cu(II) to Cu(I) and reacted with O2，it can activate the C-H bond.
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胡仁甫. « Iron and copper complexes of monoanionic N, N, O-scorpionate ligand:model study of 2-His-1-carboxylate non-heme metalloproteins ». Thesis, 2003. http://ndltd.ncl.edu.tw/handle/77122382157626726232.
Texte intégralRésumé :
碩士國立彰化師範大學
化學系
91
In order to mimic the function and active site structure of iron proteins, two scorpionate ligands : bdmpza [bis(3,5-dimethylpyrazol-1-yl) acetic acid] and bdtbpza [bis(3,5-di-tert-butylpyrazol-1-yl) acetic acid] have been synthesized. A series of iron(III) complexes, [Fe(bdmpza)Cl3] [Et4N](1), [Fe(bdmpza)(N3)3][Et4N](2), [Fe(bdmpza)(SCN)3][Et4N](3), [Fe2O(OAc)2(bdmpza)2](4), [Fe2O(bdmpza)4](5); and iron(II) complex [Fe2(bdtbpza)2Br2](6) have been synthesized. The electronic states, redox-properties, magnetic properties of complexes (4)-(5) are studied by means of UV/Vis, IR, Cyclic Voltammetry, and SQUID magnetic susceptibilities measurements. The results are comparable to other oxo-bridged iron(III) dimmer. The X-ray crystal structures further demonstrate the potential of these complexes to be used as models for mimicing active center of diiron proteins such as hemerythrin or methane monooxygenase. The physical properties and crystal structures of mononuclear iron complexes have also been characterized. The tridentate coordination mode of scorpionate ligand and the replacement of three other ligands ensure the potential of using these type of complexes to model mononuclear iron proteins with 2-His-1-carboxylate coordination environment. A series of copper(II) complexes, [Cu(bdmpza)2](7), [Cu2(bdtbpza)2Cl2](8), [Cu2(bdtbpza)2-(NO3)2](9), [Cu3(bdtbpza)2(H2O)- (OH)2Br2](10), [Cu3(bdtbpza)2(CH3O)2Br2](11), [Cu3(bdtbpza)2(NO3)4] (12), [Cu2(bdtbpzaO)2](13), [Cu(bdtbpza)(NO3)](14), and two copper(I) complexes [Cu4(bdtbpza)4Na](16)、[Cu3(bdtbpza)2Cl](17) have also been synthesized. These complexes gave rare binuclear, trinuclear or tetranuclear center. The trinuclear and tetranuclear copper complexes have low coordination number on copper centers. Importantly, in several cases, we have found that in the presence of dioxygen, the Cu(I) bdtbpza complexes have moderate activity toward aliphatic hydroxylation. The demetallation of hydroxylation product gave a new ligand, [Na2(bdtbpzaO)2](15).
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Tshabang, Never. « The chemistry of poly(methimazoly)borate complexes ». Phd thesis, 2005. http://hdl.handle.net/1885/151569.
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