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Littérature scientifique sur le sujet « Ligands scorpionates »

Auteur : Grafiati
Publié le 29 mars 2025

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Articles de revues sur le sujet "Ligands scorpionates"

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Petrosian, Artem, Pedro F. Pinheiro, Ana P. C. Ribeiro, Luísa M. D. R. S. Martins et Gonçalo C. Justino. « The Elusive Biological Activity of Scorpionates : A Useful Scaffold for Cancer Therapy ? » Molecules 29, no 23 (30 novembre 2024) : 5672. https://doi.org/10.3390/molecules29235672.

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Cancer remains a formidable challenge, requiring the constant pursuit of novel therapeutic agents and strategies. Scorpionates, known for their unique coordination properties, have recently gained attention for their anticancer potential. Traditionally applied in catalysis, these compounds have demonstrated notable cytotoxicity across various cancer cell lines, often surpassing the efficacy of conventional chemotherapeutics. This review addresses recent findings on scorpionate complexes, emphasizing the impact of metal choice and ligand design on biological activity. Copper and ruthenium scorpionates show promise, leveraging redox activity and mitochondrial disruption mechanisms to selectively induce cancer cell death. Ligand modifications, including sulfur-containing heterocycles and unsubstituted pyrazoles, have proven effective in enhancing cytotoxicity and selectivity. Furthermore, dipodal ligands show unique potential, with selective binding sites that improve stability and facilitate specific cellular interactions, such as targeting metastatic pathways. These findings highlight the largely unexplored potential of scorpionate complexes, positioning them as candidates for next-generation anticancer therapies. Continued research into structure–activity relationships and precise mechanisms of action could pave the way for developing highly potent and selective anticancer agents based on scorpionate chemistry.
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Sirianni, Eric R., Daniel C. Cummins, Glenn P. A. Yap et Klaus H. Theopold. « FcTp(R) (R=iPr ortBu) : third-generation ferrocenyl scorpionates ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 813–18. http://dx.doi.org/10.1107/s205322961601202x.

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Scorpionate (or trispyrazolylborate) ligands have seen much structural variation due to the relative ease of modifying their electronic and steric effects. Second-generation scorpionates were created by increasing the bulk in the 3-position of the pyrazole (pz) ring. A new class of third-generation scorpionates was obtained by modifying the remaining boron substituent. A series of thallium(I) and cobalt(II) complexes of the ferrocenyltris(3-R-pyrazolyl)borate ligand [FcTpR;R= isopropyl (iPr) ortert-butyl (tBu)] have been synthesized in order to expand the range of redox-active third-generation scorpionates. These are [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]thallium(I), [FeTl(C5H5)(C26H37BN6)], [ferrocenyltris(3-isopropylpyrazol-1-yl-κN2)borato]thallium(I), [FeTl(C5H5)(C23H31BN6)], chlorido[ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]cobalt(II), [CoFe(C5H5)(C26H37BN6)Cl], [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]iodidocobalt(II) benzene disolvate, [CoFe(C5H5)(C26H37BN6)I]·2C6H6, and [ferrocenyltris(3-isopropylpyrazol-1-yl-κN2)borato]iodidocobalt(II), [CoFe(C5H5)(C23H31BN6)I]. The structures demonstrate that the metal coordination site can easily be modified by using bulkier substituents at the pz 3-position.
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Martins, Luísa, Riccardo Wanke, Telma Silva, Armando Pombeiro, Paul Servin, Régis Laurent et Anne-Marie Caminade. « Novel Methinic Functionalized and Dendritic C-Scorpionates ». Molecules 23, no 12 (23 novembre 2018) : 3066. http://dx.doi.org/10.3390/molecules23123066.

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The study of chelating ligands is undoubtedly one of the most significant fields of research in chemistry. The present work is directed to the synthesis of new functionalized derivatives of tripodal C-scorpionate compounds. Tris-2,2,2-(1-pyrazolyl)ethanol, HOCH2C(pz)3 (1), one of the most important derivatives of hydrotris(pyrazolyl)methane, was used as a building block for the synthesis of new functionalized C-scorpionates, aiming to expand the scope of this unexplored class of compounds. The first dendritic C-scorpionate was successfully prepared and used in the important industrial catalytic reactions, Sonogashira and Heck C-C cross-couplings.
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Nicolas, Emmanuel, Thibault Cheisson, G. Bas de Jong, Cornelis G. J. Tazelaar et J. Chris Slootweg. « A new synthetic route to the electron-deficient ligand tris(3,4,5-tribromopyrazol-1-yl)phosphine oxide ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 846–49. http://dx.doi.org/10.1107/s2053229616015035.

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The anionic tris(pyrazolyl)borates, or scorpionates, have proven to be extremely useful ligands. Neutral tris(pyrazolyl)methane ligands, however, are difficult to prepare and require numerous purification steps for a number of substitution patterns. We have previously outlined two different routes for accessing neutral tris(pyrazolyl) ligands. We describe here an adaptation of the previously published procedures for the synthesis of the electron-poor ligand tris(3,4,5-tribromopyrazol-1-yl)phosphine oxide, C9Br9N6OP. Similar electron-deficient ligands have been proven to unlock unique chemistry for the anionic scorpionates. The title perbrominated tris(pyrazolyl)phosphine oxide displays a network of halogen bonds in the solid state. All the bonds in the pyrazole ring are rather similar to the reported borate analogues, which makes this molecule promising as a ligand for applications where very electron-poor metal complexes are required.
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Takayama, Tomoaki, Jun Nakazawa et Shiro Hikichi. « A pseudotetrahedral nickel(II) complex with a tridentate oxazoline-based scorpionate ligand : chlorido[tris(4,4-dimethyloxazolin-2-yl)phenylborato]nickel(II) ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 842–45. http://dx.doi.org/10.1107/s2053229616012183.

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Poly(pyrazol-1-yl)borates have been utilized extensively in coordination compounds due to their high affinity toward cationic metal ions on the basis of electrostatic interactions derived from the mononegatively charged boron centre. The original poly(pyrazol-1-yl)borates, christened `scorpionates', were pioneered by the late Professor Swiatoslaw Trofimenko and have expanded to include various borate ligands with N-, P-, O-, S-, Se- and C-donors. Scorpionate ligands with boron–carbon bonds, rather than the normal boron–nitrogen bonds, have been developed and in these new types of scorpionate ligands, amines and azoles, such as pyridines, imidazoles and oxazolines, have been employed as N-donors instead of pyrazoles. Furthermore, a variety of bis- and tris(oxazolinyl)borate ligands, including chiral ones, have been developed. Tris(oxazolin-2-yl)borates work as facially capping tridentate chelating ligands in the same way as tris(pyrazol-1-yl)borates. In the title compound, [Ni(C21H29BN3O3)Cl], the NiIIion is coordinated by three N atoms from the facially capping tridentate chelating tris(4,4-dimethyloxazolin-2-yl)phenylborate ligand and a chloride ligand in a highly distorted tetrahedral geometry. The Ni—Cl bond length [2.1851 (5) Å] is comparable to those found in a previously reported tris(3,5-dimethylpyrazol-1-yl)hydroborate derivative [2.1955 (18) and 2.150 (2) Å]. The molecular structure deviates fromC3vsymmetry due to the structural flexibility of the tris(4,4-dimethyloxazolin-2-yl)phenylborate ligand.
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Wang, Guocang, Anurag Noonikara-Poyil, Israel Fernández et H. V. Rasika Dias. « Iron pentacarbonyl ligands on silver scorpionates ». Chemical Communications 58, no 19 (2022) : 3222–25. http://dx.doi.org/10.1039/d1cc06859h.

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Andrade, Marta A., et Luísa M. D. R. S. Martins. « Novel Chemotherapeutic Agents - The Contribution of Scorpionates ». Current Medicinal Chemistry 26, no 41 (8 janvier 2020) : 7452–75. http://dx.doi.org/10.2174/0929867325666180914104237.

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: The development of safe and effective chemotherapeutic agents is one of the uppermost priorities and challenges of medicinal chemistry and new transition metal complexes are being continuously designed and tested as anticancer agents. Scorpionate ligands have played a great role in coordination chemistry, since their discovery by Trofimenko in the late 1960s, with significant contributions in the fields of catalysis and bioinorganic chemistry. Scorpionate metal complexes have also shown interesting anticancer properties, and herein, the most recent (last decade) and relevant scorpionate complexes reported for application in medicinal chemistry as chemotherapeutic agents are reviewed. The current progress on the anticancer properties of transition metal complexes bearing homo- or hetero- scorpionate ligands, derived from bis- or tris-(pyrazol-1-yl)-borate or -methane moieties is highlighted.
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Gardinier, James R., Alex R. Treleven, Kristin J. Meise et Sergey V. Lindeman. « Accessing spin-crossover behaviour in iron(ii) complexes of N-confused scorpionate ligands ». Dalton Transactions 45, no 32 (2016) : 12639–43. http://dx.doi.org/10.1039/c6dt01898j.

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Goldsworthy, Joseph, Simon D. Thomas, Graham J. Tizzard, Simon J. Coles et Gareth R. Owen. « Adding to the Family of Copper Complexes Featuring Borohydride Ligands Based on 2-Mercaptopyridyl Units ». Inorganics 7, no 8 (24 juillet 2019) : 93. http://dx.doi.org/10.3390/inorganics7080093.

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Borohydride ligands featuring multiple pendant donor functionalities have been prevalent in the chemical literature for many decades now. More recent times has seen their development into new families of so-called soft scorpionates, for example, those featuring sulfur based donors. Despite all of these developments, those ligands containing just one pendant group are rare. This article explores one ligand family based on the 2-mercaptopyridine heterocycle. The coordination chemistry of the monosubstituted ligand, [H3B(mp)]− (mp = 2-mercaptopyridyl), has been explored. Reaction of Na[BH3(mp)] with one equivalent of Cu(I)Cl in the presence of either triphenylphosphine or tricyclohexylphosphine co-ligands leads to the formation of [Cu{H3B(mp)}(PR3)] (R = Ph, 1; Cy, 2), respectively. Structural characterization confirms a κ3-S,H,H coordination mode for the borohydride-based ligand within 1 and 2, involving a dihydroborate bridging interaction (BH2Cu) with the copper centers.
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Trofimenko, Swiatoslaw, Fernando Jové et Glenn P. A. Yap. « An unusual bis-heteroscorpionate complex with anomalous ligands : [tris(3,4-dibromo-5-phenylpyrazolyl)hydroborato][hydrotris(3-neopentylpyrazolyl)borato]nickel(II) ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 802–5. http://dx.doi.org/10.1107/s2053229616001376.

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Tridentate trispyrazolylborate (Tp) ligands, introduced by Trofimenko in 1966, have been widely utilized in metal coordination chemistry because of the relatively facile synthetic modification of their electronic and steric factors. The title heteroscorpionate, [Ni(C27H16BBr6N6)(C24H40BN6)], features one ligand, namely hydrotris(3-neopentylpyrazolyl)borate, that has previously displayed variable steric effects, and a brominated ligand, namely tris(3,4-dibromo-5-phenylpyrazolyl)hydroborate, that, atypical in trispyrazolylborate chemistry, coordinates such that the less bulky pyrazole substituent is oriented facing toward the metal ion. The potential molecular threefold symmetry in scorpionates can allow axial chirality. Although crystallized in the centrosymmetricP\overline{1} space group, a closer inspection of the structure of the title compound reveals axial diastereomers.
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Thèses sur le sujet "Ligands scorpionates"

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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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Wang, Zekun. « La synthèse et la catalyse de complexes organométaliques de cobalt (III) de ligands chélateurs scorpionates ». Electronic Thesis or Diss., Strasbourg, 2025. http://www.theses.fr/2025STRAF004.

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Cette thèse porte sur la synthèse et les applications catalytiques des complexes de cobalt(III) contenant des ligands chélatants de type scorpionate. Des ligands tris(pyrazolyl)borate (Tp) ont été utilisés pour former des complexes de cobalt présentant une diversité de propriétés structurelles et électroniques. Une exploration systématique de ces complexes révèle leur potentiel dans les transformations catalytiques, notamment dans les réactions de couplage carbone-carbone. En outre, le phénomène de spin-crossover observé dans les complexes de cobalt permet des transitions dynamiques entre les états de spin élevé et de spin faible, influençant de manière significative les mécanismes réactionnels et l’efficacité catalytique. Cette propriété facilite l’activation des substrats et des intermédiaires, tout en abaissant les barrières énergétiques des étapes clés de la catalyse. Ces caractéristiques permettent des voies réactionnelles efficaces dans des conditions douces, mettant en avant le potentiel du cobalt en tant que catalyseur multifonctionnel et durable
This thesis focuses on the synthesis and catalytic applications of cobalt(III) complexes containing scorpionate chelating ligands. Tris(pyrazolyl)borate (Tp) ligands were utilized to form cobalt complexes with diverse structural and electronic properties. Systematic exploration of these complexes reveals their potential in catalytic transformations, particularly in carbon-carbon coupling reactions. The spin-crossover phenomenon observed in cobalt complexes allows for dynamic transitions between high-spin and low-spin states, significantly influencing reaction mechanisms and catalytic efficiency. This property facilitates the activation of substrates and intermediates, lowering energy barriers in key catalytic steps. Additionally, the oxidation of cobalt to higher oxidation states enhances its catalytic performance. These features enable efficient reaction pathways under mild conditions, highlighting cobalt's potential as a multifunctional and sustainable catalyst
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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.

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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 imidazol‐2‐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.
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Rajasekharan, Nair Rajeev. « Exploring the chemistry of soft scorpionate ligands ». Thesis, University of Strathclyde, 2013. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=24333.

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Alkylation of the soft scorpionate anions, TmR, Tbz and tzTtz have been successfully carried out. The resulting cationic species of TmMe were fully characterised. However, the formation of the cationic species is not always favourable and the alkylated products of Tbz and tzTtz were found to be unstable. The structures and degradation pathways of the three species were interrogated using ab-initio DFT calculations. This suggested that the B-N bond can lengthen when the scorpionate is alkylated and that this leads to thio-imidazole elimination. This work was extended to the synthesis of cyclic ring system initially by linking two sulphurs in the anion using dihalo-alkane species. Ring formation can also be effected using mild oxidising agents and treatment of TmMe and TmPh with NO+ and I₂ leads to the synthesis of a series of unique polycyclic heterocycles. The importance of B-N bond elongation to complex stability is investigated further using the Tbz anion. As expected Tbz is unable to form complexes with the hard metals e.g. cobalt. Treatment with soft metals (mercury, antimony and bismuth) does produce complexes but these are not stable. These metal complexes rearrange to form a new class of polycyclic rings. Studies using NO+ are extended to its chemistry of soft scorpionate metal complexes. A study was conducted which sought to use ruthenium complexes as nitric oxide scavengers. This chemistry failed to materialise and NO+ acts as a mild oxidising agent rather than a π acceptor with these species. % Buried volume analysis is performed using a series of soft scorpionates (TmR R = Me, iPr, tBu, and Ph) to calculate the steric demand of the ligands at the central metal atom. The study reveals that there is a modest effect when the scorpionate is supporting a four coordinated metal (e.g. zinc). However, for six coordinated metals (e.g. manganese as its tricarbonyl) the scorpionate has minimal influence.
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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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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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Garnier, Delphine. « Open-shell Coordination Compounds based on Cyanide and Scorpionate Ligands ». Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066296/document.

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Cette thèse porte sur la synthèse et la caractérisation de complexes octaédrique de fer(II) et fer(III) coordinés par un ligand tridente de type scorpionate (symétrie fac) et par trois ligands cyanures. Leur utilisation en tant que metalloligand face à des ions métalliques partiellement bloqués est étudiée. Les ligands cyanures, de par leur caractère ambidente, permettent un accès facile aux espèces hétérobimétalliques. De plus, ces ligands sont connus pour transmettre efficacement l'interaction d'échange magnétique et donc pour favoriser la communication électronique intramoléculaire entre les ions métalliques qu'ils relient. La fonctionalisation des ligands scorpionates permet de contrôler les propriétés électroniques intrinsèques des complexes précurseurs de fer, et donc de moduler les propriétés des espèces polynucléaires obtenues à partir de ces dernières par auto-assemblage. Dans cette thèse, un intérêt particulier est porté aux systèmes {FeCo} en raison de leur capacité à présenter une bistabilité électronique (propriétés photomagnétiques ou de molécules/chaines aimants). Les systèmes cyanuré {FeCo} sont particulièrement adaptés pour l'observation de réarrangements électroniques thermo- et/ou photo-induit, comme en témoignent le nombre important de composés cyanurés photomagnétiques dans la littérature
The work presented in this PhD dissertation focuses on the synthesis and the characterisation of octahedral iron(II) and iron(III) complexes coordinated by a tridentate ligand of the scorpionate family (fac- geometry) and three cyanide ligands. Their use as metalloligands in respect to partially blocked metal ions is studied. Because of their ambidentate character, cyanide ligands open the door to facile synthesis of heterobimetallic species. Moreover, these ligands are known to be efficient magnetic exchange interaction transmitter, thus favouring intramolecular electronic communication between the metal ions they are bridging. The functionalisation of scorpionate ligands allows control over the intrinsic electronic properties of the iron precursor complexes, thus allows to tune the properties of the obtained polynuclear species from the latter by self-assembly. In this PhD dissertation, a particular interest was taken in {FeCo} systems because of their potential ability to exhibit electronic bistability (photomagnetic properties or SMM/SCM behaviour). Cyanide-bridged {FeCo} systems are particularly suitable for the observation of thermally or light-induced electron rearrangements, as testified by the wide range of photomagnetic cyanide-bridged compounds in the literature
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Jacquot, de Rouville Henri-Pierre. « Synthèse de molécules technomimétiques pour des applications en nanomécanique ». Toulouse 3, 2010. http://thesesups.ups-tlse.fr/1019/.

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Deux machines moléculaires technomimétiques, dont la forme et la fonction miment des objets macroscopiques, ont été développées au cours de cette thèse : un moteur moléculaire et un nanovéhicule. La première de ces machines est destinée à générer un mouvement de rotation azimutal. C'est une famille de complexes de ruthénium coordinés par un ligand de type scorpionate jouant le rôle de stator et par un ligand pentaphénylcyclopentadiényl jouant le rôle de rotor. Afin de favoriser un mouvement de rotation unidirectionnel du rotor, l'introduction de chiralité a été effectuée dans la structure de la molécule. De plus, un stator fonctionnalisé par un groupement azobenzène et son complexe de ruthénium modèle ont été synthétisés afin d'arrêter de manière contrôlée la rotation du rotor. La seconde machine est quant à elle destinée à générer un mouvement de rotation altitudinal. Pour cela, une nouvelle génération de roues a été élaborée à partir de fragments subphthalocyanine dont la forme de bol ne présente pas d'interactions trop importantes avec la surface. Dès lors, la synthèse d'un nanovéhicule a été envisagée autour d'un plateau polyaromatique
Two technomimetic molecular machines, which have the shape and the function of macroscopic objects, were developed during this thesis: a molecular motor and a nanovehicle. The first one was designed in order to control an azimutal rotational motion. This machine is based on a family of ruthenium complexes coordinated by a scorpionate ligand acting as a stator and a pentaphenylcyclopentadienyl ligand acting as a rotor. In order to favor a unidirectional rotation of the rotor, introduction of chirality was achieved in the design of the molecule. Besides, a stator functionalized with an azobenzene functional group and its ruthenium model complex were synthesized in order to lock the rotation of the rotor in a controlled manner. The second machine was designed to control an altitudinal rotational motion. To achieve this goal, a new generation of wheels was synthesised based on subphthalocyanine fragments which have a bowl shape structure avoiding too many interactions with the surface. The synthesis of a nanovehicle was considered around a polyaromatic core
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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
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Livres sur le sujet "Ligands scorpionates"

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Swiatoslaw, Trofimenko, dir. Scorpionates II : Chelating borate ligands. London : Imperial College Press, 2008.

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Trofimenko, Swiatoslaw. Scorpionates : The coordination chemistry of polypyrazolborate ligands. London : Imperial College Press, 1999.

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Ghana, Priyabrata. Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands. Cham : Springer International Publishing, 2019. http://dx.doi.org/10.1007/978-3-030-02625-7.

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Scorpionates II : Chelating Borate Ligands. Imperial College Press, 2008.

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Trofimenko, Swiatoslaw. Scorpionates : Polypyrazolylborate Ligands and Their Coordination Chemistry. World Scientific Publishing Company, 1999.

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Scorpionates : The coordination chemistry of polypyrazolylborate ligands. River Edge, NJ : Imperial College Press, 1999.

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Trofiemenko, Swiatoslaw. Scorpionates : The Coordination Chemistry of Polypyrazolylborate Ligands. World Scientific Publishing Co Pte Ltd, 1999.

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Scorpionates II - Chelating Borate Ligands : Dedicated to Swiatoslaw Trofimenko. World Scientific Publishing Co Pte Ltd, 2008.

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Ghana, Priyabrata. Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands. Springer, 2018.

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Chapitres de livres sur le sujet "Ligands scorpionates"

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Ghana, Priyabrata. « Introduction ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 1–15. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_1.

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Ghana, Priyabrata. « Access to the First NHC-Stabilized Disilavinylidene ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 179–91. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_10.

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Ghana, Priyabrata. « Summary ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 195–202. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_11.

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Ghana, Priyabrata. « Outlook ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 203–5. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_12.

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Ghana, Priyabrata. « Experimental Section ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 207–97. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_13.

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Ghana, Priyabrata. « Closed Shell Heavier Tetrylidyne Complexes of Group 6 Metals ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 19–75. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_2.

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Ghana, Priyabrata. « Open-Shell Heavier Tetrylidyne Complexes of Group 6 Transition Metals ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 77–81. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_3.

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Ghana, Priyabrata. « Germylidyne Mediated C–C Coupling Reaction of Isonitriles—Formation of an N-Heterocyclic Germylene ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 83–86. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_4.

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Ghana, Priyabrata. « A New Method for the Synthesis of Manganese Tetrylidyne Complexes ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 87–102. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_5.

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Ghana, Priyabrata. « An Open-Shell Manganese Stannylidyne Comprising of a Tin-Centered Unpaired Electron ». Dans Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands, 103–13. Cham : Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_6.

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