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Articles de revues sur le sujet « Ligands scorpionates »

Auteur : Grafiati
Publié le 29 mars 2025

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1

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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Pettinari, Claudio, Augusto Cingolani, Giancarlo Gioia Lobbia, Fabio Marchetti, Domenico Martini, Maura Pellei, Riccardo Pettinari et Carlo Santini. « Copper and silver derivatives of scorpionates and related ligands ». Polyhedron 23, no 2-3 (janvier 2004) : 451–69. http://dx.doi.org/10.1016/j.poly.2003.11.033.

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12

Su, Wei-Jia, et Lan-Chang Liang. « Elusive Scorpionates : C3-Symmetric, Formally Dianionic, Facially Tridentate Ligands ». Inorganic Chemistry 57, no 2 (27 décembre 2017) : 553–56. http://dx.doi.org/10.1021/acs.inorgchem.7b02884.

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13

Dias, H. V. Rasika, et Naveen Kulkarni. « The silver(I) complex [HB{3-(CF3),5-(CH3)Pz}3]AgNCCH3supported by a partially fluorinated scorpionate ligand ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 853–56. http://dx.doi.org/10.1107/s2053229616006744.

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Tris(pyrazolyl)borates are used extensively in metal coordination chemistry and belong to a class of ligands generally referred to as scorpionates. The steric and electronic properties of these ligands can be modified quite easily by varying the substituents on the 3-, 4-, and 5-positions of the pyrazolyl moieties on the B atom. Fluorinated tris(pyrazolyl)borates are useful in the stabilization of rare silver(I) complexes. The silver(I) adduct (acetonitrile-κN){tris[5-methyl-3-(trifluoromethyl)pyrazol-1-yl-κN2]hydroborato}silver(I), [Ag(C15H13BF9N6)(CH3CN)] or [HB{3-(CF3),5-(CH3)Pz}3]AgNCCH3, was obtained by treating [HB{3-(CF3),5-(CH3)Pz}3]Na with CF3SO3Ag in the presence of acetonitrile, and was isolated in 85% yield. Single-crystal X-ray diffraction analysis reveals that the AgIcenter has a pseudo-tetrahedral all-nitrogen coordination sphere, and is supported by a tris(pyrazolyl)borate ligand that binds to the AgIcenter in a κ3-fashion.
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Edelmann, Frank T. « Versatile Scorpionates—New Developments in the Coordination Chemistry of Pyrazolylborate Ligands ». Angewandte Chemie International Edition 40, no 9 (4 mai 2001) : 1656–60. http://dx.doi.org/10.1002/1521-3773(20010504)40:9<1656 ::aid-anie16560>3.0.co;2-q.

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15

Wang, Denan, James R. Gardinier et Sergey V. Lindeman. « Iron(ii) tetrafluoroborate complexes of new tetradentate C-scorpionates as catalysts for the oxidative cleavage of trans-stilbene with H2O2 ». Dalton Transactions 48, no 38 (2019) : 14478–89. http://dx.doi.org/10.1039/c9dt02829c.

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Edelmann, Frank T. « ChemInform Abstract : Versatile Scorpionates - New Developments in the Coordination Chemistry of Pyrazolylborate Ligands. » ChemInform 32, no 34 (25 mai 2010) : no. http://dx.doi.org/10.1002/chin.200134137.

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Meinholz, Margret M., Sushil K. Pandey, Stephan M. Deuerlein et Dietmar Stalke. « Access to new Janus head ligands : linking sulfur diimides and phosphanes for hemilabile tripodal scorpionates ». Dalton Transactions 40, no 8 (2011) : 1662. http://dx.doi.org/10.1039/c0dt00665c.

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Infantes, Lourdes, Rosa M. Claramunt, Dionisia Sanz, Ibon Alkorta et José Elguero. « The structures of two scorpionates : thallium tetrakis(3-phenyl-1H-pyrazol-1-yl)borate and potassium tetrakis(3-cyclopropyl-1H-pyrazol-1-yl)borate ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 819–25. http://dx.doi.org/10.1107/s2053229616007385.

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The introduction of poly(1H-pyrazolyl)borate anions, better known as scorpionates, as negatively charged ligands for a great diversity of metal cations has had a tremendous influence in coordination chemistry. The structures of two salts of tetrakispyrazolylborate, namely [tetrakis(3-phenyl-1H-pyrazol-1-yl)borato]thallium(I), [Tl(C36H28BN8)], andcatena-poly[potassium-[μ2-tetrakis(3-cyclopropyl-1H-pyrazol-1-yl)borato]], [K(C24H28BN8)]n, have been determined at 296 K in the monoclinicP21/candC2/cspace groups, respectively. In their crystal structures, the thallium salt presents discrete molecular motifs, while the potassium salt shows infinite polymeric chains. The13C and15N CPMAS (cross polarization magic angle spinning) NMR spectra of these compounds were recorded and the chemical shifts compared with theoretically calculated ones at the GIAO/B3LYP/6-311++G(d,p) level. Both techniques are complementary and mutually consistent.
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Bailey, Philip J., Nicola L. Bell, Lim Li Gim, Tai Yucheng, Nicholas Funnell, Fraser White et Simon Parsons. « “Twisted” scorpionates : synthesis of a tris(2-pyridonyl)borate (Thp) ligand ; lessons in the requirements for successful B(L2D)3 type ligands ». Chemical Communications 47, no 42 (2011) : 11659. http://dx.doi.org/10.1039/c1cc14473a.

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Otero, Antonio, Juan Fernández-Baeza, Agustín Lara-Sánchez, Antonio Antiñolo, Juan Tejeda, Emilia Martínez-Caballero, Isabel Márquez-Segovia, Isabel López-Solera, Luis F. Sánchez-Barba et Carlos Alonso-Moreno. « Versatile Scorpionates and New Developments in the Denticity Changes of NNCp Hybrid Scorpionate/Cyclopentadienyl Ligands in Sc and Y Compounds : From κ1-Nη5-Cp to κ2-NNη5-Cp ». Inorganic Chemistry 47, no 11 (juin 2008) : 4996–5005. http://dx.doi.org/10.1021/ic800267v.

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Plasseraud, Laurent, et Hélène Cattey. « s-Block metal scorpionates – A new sodium hydrido-tris(3,5-dimethyl-1-pyrazolyl)borate salt showing an unusual core stabilized by bridging and terminal O-bonded DMSO ligands ». Main Group Metal Chemistry 43, no 1 (21 juin 2020) : 102–10. http://dx.doi.org/10.1515/mgmc-2020-0012.

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AbstractDissolution of [(μ-Me2CO)3(NaTp*)2] (1) (Tp* = hydrido-tris(3,5-dimethyl-1-pyrazolyl)borate) in DMSO at room temperature leads to the growth of colourless crystals characterized as the new salt [Na2Tp*(μ-Me2SO)3(Me2SO)3] [NaTp*2] (2). 2 crystallized in the trigonal space group R3 with Z = 3, a = 14.1227(2) Å, b = 14.1227(10) Å, c = 33.9685(2) Å, and V = 5867.35(17) Å3. Interestingly, anion and cation of 2 both contain the Tp* ligand. Moreover, the cationic moiety highlights an unusual sodium atom hexacoordinated by six DMSO molecules acting as O-bonded ligands. Three of which exhibit a bridging coordination mode and three are in terminal position. To the best of our knowledge, the framework of [Na2Tp*(μ-Me2SO)3(Me2SO)3] is unprecedented.
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Cummins, Daniel C., Glenn P. A. Yap et Klaus H. Theopold. « Scorpionates of the “Tetrahedral Enforcer” Variety as Ancillary Ligands for Dinitrogen Complexes of First Row Transition Metals (Cr-Co) ». European Journal of Inorganic Chemistry 2016, no 15-16 (18 février 2016) : 2349–56. http://dx.doi.org/10.1002/ejic.201501326.

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Pellei, Maura, Grazia Papini, Giancarlo Gioia Lobbia, Simone Ricci, Muhammed Yousufuddin, H. V. Rasika Dias et Carlo Santini. « Scorpionates bearing nitro substituents : mono-, bis- and tris-(3-nitro-pyrazol-1-yl)borate ligands and their copper(i) complexes ». Dalton Transactions 39, no 38 (2010) : 8937. http://dx.doi.org/10.1039/c0dt00474j.

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Green, William L., Eric R. Sirianni, Glenn P. A. Yap et Charles G. Riordan. « Steric and electronic factor comparisons in hydrotris(3-phenylpyrazolyl)borate nickel(II) aryloxides ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 791–96. http://dx.doi.org/10.1107/s2053229616001789.

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Hydrotris(pyrazolyl)borate (Tp) ligands, also known as scorpionates, are potent tridentate donors that effectively bind metal ions in a face-capping array. Hydrotris(3-phenylpyrazolyl)borate enforces a tetrahedral environment on NiIIto model metalloenzymes. The syntheses and structural characterizations of a number of [hydrotris(3-phenylpyrazolyl)borato]nickel(II) aryloxides were performed to provide insight into the environment of the model active site; these compounds are chlorido[hydrotris(3-phenylpyrazolyl-κN2)borato](3-phenyl-1H-pyrazole-κN2)nickel(II) chloroform monosolvate, [Ni(C27H22BN6)Cl(C9H8N2)]·CHCl3, (2), [hydrotris(3-phenylpyrazolyl-κN2)borato](phenolato-κO)nickel(II), [Ni(C27H22BN6)(C6H5O)], (3), (2,6-dimethylphenolato-κO)[hydrotris(3-phenylpyrazolyl-κN2)borato]nickel(II) [Ni(C27H22BN6)(C8H9O)], (4), (4-tert-butylphenolato-κO)[hydrotris(3-phenylpyrazolyl-κN2)borato]nickel(II), [Ni(C27H22BN6)(C10H13O)], (5), and [hydrotris(3-phenylpyrazolyl-κN2)borato](phenolato-κO)(tetrahydrofuran-κO)nickel(II) tetrahydrofuran monosolvate, [Ni(C27H22BN6)(C6H5O)(C4H8O)]·C4H8O, (6). Alkyl groups,e.g. tert-butyl in (5) and methyl in (4), electronically activate the aryloxide group to intramolecular π–π stacking but can be frustrated by steric encumbrance at the interacting ring faces. The flexibility at the nickel coordination site, afforded by the uncrowded B atom of the TpPhligand, allows tetrahydrofuran coordination in the phenolate compound.
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Kunz, Kerstin, Michael Bolte, Hans-Wolfram Lerner et Matthias Wagner. « Photochemistry of Cymantrenyl Scorpionates : Formation of a Novel Tritopic Cyclopentadienyl/Scorpionate Hybrid Ligand ». Organometallics 28, no 10 (25 mai 2009) : 3079–87. http://dx.doi.org/10.1021/om900190r.

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Jackson, Miriam, Simon D. Thomas, Graham J. Tizzard, Simon J. Coles et Gareth R. Owen. « Synthesis and Structural Characterization of Copper Complexes Containing “R-Substituted” Bis-7-Azaindolyl Borate Ligands ». Molecules 28, no 12 (17 juin 2023) : 4825. http://dx.doi.org/10.3390/molecules28124825.

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The coordination chemistry of scorpionate ligands based on borates containing the 7-azaindole heterocycle is relatively unexplored. Thus, there is a requirement to further understand their coordination chemistry. This article outlines the synthesis and characterization of a family of complexes containing anionic flexible scorpionate ligands of the type [(R)(bis-7-azaindolyl)borohydride]− ([RBai]−), where R = Me, Ph or naphthyl. The three ligands were coordinated to a series of copper(I) complexes containing a phosphine co-ligand to form the complexes, [Cu(MeBai)(PPh3)] (1), [Cu(PhBai)(PPh3)] (2), [Cu(NaphthBai)(PPh3)] (3), [Cu(MeBai)(PCy3)] (4), [Cu(PhBai)(PCy3)] (5) and [Cu(NaphthBai)(PCy3)] (6). Additional copper(II) complexes, namely, [Cu(MeBai)2] (7) and [Cu(PhBai)2] (8), were obtained during attempts to obtain single crystals from complexes 4 and 2, respectively. Complexes 7 and 8 were also prepared independently from CuCl2 and two equivalents of the corresponding Li[RBai] salt alongside an additional complex, namely, [Cu(NaphthBai)2] (9). The copper(I) and copper(II) complexes were characterized using spectroscopic and analytical methods. Furthermore, a crystal structure was obtained for eight of the nine complexes. In all cases, the boron-based ligand was found to bind to the metal centers via a κ3-N,N,H coordination mode.
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Tăbăcaru, Aurel, Rais Ahmad Khan, Giulio Lupidi et Claudio Pettinari. « Synthesis, Characterization and Assessment of the Antioxidant Activity of Cu(II), Zn(II) and Cd(II) Complexes Derived from Scorpionate Ligands ». Molecules 25, no 22 (13 novembre 2020) : 5298. http://dx.doi.org/10.3390/molecules25225298.

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Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp4Bo,5Me), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTpa) and potassium hydrotris(3-tert-butyl- pyrazolyl)borate (KTptBu), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp4Bo,5Me)2] (M = Cu, 1; Zn, 4; Cd, 7), [M(Tpa)2] (M = Cu, 2; Zn, 5; Cd, 8), [Cu(HpztBu)3Cl2] (3), [Zn(TptBu)Cl] (6) and [Cd(BptBu)(HpztBu)Cl] (9). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand TptBu during the synthesis of the Cu(II) complex 3 and the Cd(II) complex 9, respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH·), 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+·), hydroxyl (HO·), nitric oxide (NO·), superoxide (O2−) and peroxide (OOH·) radicals. In particular, the complex [Cu(Tpa)2]⋅0.5H2O (2) exhibited significant antioxidant activity, as good and specific activity against superoxide (O2−·), (IC50 values equal to 5.6 ± 0.2 μM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase).
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Martini, Petra, Micol Pasquali, Alessandra Boschi, Licia Uccelli, Melchiore Giganti et Adriano Duatti. « Technetium Complexes and Radiopharmaceuticals with Scorpionate Ligands ». Molecules 23, no 8 (15 août 2018) : 2039. http://dx.doi.org/10.3390/molecules23082039.

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Scorpionate ligands have played a crucial role in the development of technetium chemistry and, recently, they have also fueled important advancements in the discovery of novel diagnostic imaging agents based on the γ-emitting radionuclide technetium-99m. The purpose of this short review is to provide an illustration of the most general and relevant results in this field, however without being concerned with the details of the analytical features of the various compounds. Thus, emphasis will be given to the description of the general features of technetium complexes with scorpionate ligands including coordination modes, structural properties and an elementary bonding description. Similarly, the most relevant examples of technetium-99m radiopharmaceuticals derived from scorpionate ligands and their potential interest for nuclear imaging will be summarized.
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Akef Ibrahim Alhmaideen, Akef Ibrahim Alhmaideen, Hamzeh M. Abdel Halim Hamzeh M Abdel Halim et Assala A. Al Twal and Adnan S. Abu Surrah Assala A Al Twal and Adnan S Abu Surrah. « Synthesis of New Series of Transition Metal Complexes with Poly (Pyrazolyl) Borates ». Journal of the chemical society of pakistan 45, no 4 (2023) : 294. http://dx.doi.org/10.52568/001289/jcsp/45.04.2023.

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In structuring catalysis enzyme and chemistry, tridentate ligands and Scorpionate ligands are of significant worth. This study presents the synthesis of a tris(pyrazolyl)borate ligand to be utilized in transition metal complexes as possible redox shuttles. Complexes of general formula [AgTp], [MIIITp (Cl2)] (M = Fe, Co), Tp = tri (1-pyrazolyl) borohydride and [AgTp*], [FeIIITp*(Cl2)], Tp* = tris (3, 5-dimethyl-1-pyrazolyl) borohydride were synthesized and characterized in solid state. The Tp ligands were considered triply coordinated with the metal center with two bounded chloride atoms as per the information gathered from spectroscopic information. Entire preparations and operations were performed under argon using common Schlenk procedures. Elemental analysis was performed using (the EURO EA instrument). Thermolysis shows that the Tp ligand decomposes around 100oC and above 300oC for some complexes. The composites were simple to compose, yielded high yields, and were reasonably air sensitive. This study has examined the synthesis of a tris(pyrazolyl)borohydride ligand to develop an iron complex. Further studies conducting electrochemical tests should be carried out to demonstrate the effectiveness of this likely redox mediator.
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Smith, Jeremy M. « STRONGLY DONATING SCORPIONATE LIGANDS ». Comments on Inorganic Chemistry 29, no 5-6 (4 décembre 2008) : 189–233. http://dx.doi.org/10.1080/02603590802590080.

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., Eishika, Himani . et Ridhi . « Review of Synthesis and Characterization of Cu (I) Complexes ». International Journal of Research and Review 11, no 1 (10 janvier 2024) : 195–209. http://dx.doi.org/10.52403/ijrr.20240121.

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d-block metals show great promise in inorganic catalytic research. Particularly, copper, d9 metal has contributed to catalytic properties of its complexes. A series of copper complexes was synthesized and structurally characterized. The copper (I) complexes of this series were investigated in regard to their reactivity towards dioxygen using stopped-flow techniques. For most complexes no “oxygen adduct” complexes as intermediates could be detected. In this article, some complexes of Cu (I) have been included and the ligands on which work had been done are mentioned below: 1,5-bis(benzimidazole-2-yl)-3-thiapentane Tridentate di-pyrazole -3,6-di-tert-butyl-carbazole (N, N, N-Pincer ligand) Methyl isocyanate N4Cu Tris(pyrazolyl) hydroborate ligand Scorpionate ligand Phenanthroline Tripodal amine ligands Triazole derivatives Keywords: BBES (1,5-bis(benzimidazole-2-yl)-3-thiapentane), MeIN (Methyl isocyanate), CuSCN (copper thiocyanate), PPh3(triphenyl phosphine), PCy3(tricyclohexyl phosphine), TptBuPh (tris[3-(p-tert-butylphenyl)], Tp (tris pyrazolyl hydroborate), Me4-p,3,3 (3,3-dimethylaminopropyl-(2-methylenpyridyl)-amine), Me2-pp3 (3-dimethylaminopropyl-bis(2-methylenpyridyl)-amine)
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Albertin, Gabriele, Stefano Antoniutti, Marco Bortoluzzi, Jesús Castro et Lidia Marzaro. « Diazoalkane complexes of ruthenium with tris(pyrazolyl)borate and bis(pyrazolyl)acetate ligands ». Dalton Transactions 44, no 35 (2015) : 15470–80. http://dx.doi.org/10.1039/c5dt02113h.

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Duriska, M. B., S. R. Batten, J. Lu, P. Jensen, H. Adams, G. M. Davies, J. C. Jeffery, G. R. Motson et M. D. Ward. « Crystal engineering with scorpionate ligands ». Acta Crystallographica Section A Foundations of Crystallography 61, a1 (23 août 2005) : c356. http://dx.doi.org/10.1107/s0108767305084850.

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Rheingold, Arnold L., Brian S. Haggerty, Louise M. Liable-Sands et Swiatoslaw Trofimenko. « N,O-Polydentate Scorpionate Ligands ». Inorganic Chemistry 38, no 26 (décembre 1999) : 6306–8. http://dx.doi.org/10.1021/ic990881e.

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Tüchler, Michael, Melanie Ramböck, Simon Glanzer, Klaus Zangger, Ferdinand Belaj et Nadia Mösch-Zanetti. « Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands ». Inorganics 7, no 2 (19 février 2019) : 24. http://dx.doi.org/10.3390/inorganics7020024.

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Scorpionate ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based scorpionate ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution.
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Suter, Riccardo, Mona Wagner, Lorenzo Querci, Riccardo Conti, Zoltán Benkő et Hansjörg Grützmacher. « 1,3,4-Azadiphospholides as building blocks for scorpionate and bidentate ligands in multinuclear complexes ». Dalton Transactions 49, no 24 (2020) : 8201–8. http://dx.doi.org/10.1039/d0dt01864c.

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Yoshida, Jun, Keisuke Sugawara, Hidetaka Yuge et Jun Okabayashi. « Bis(acetylacetonato)bis(pyrazolato)ruthenate(iii) as a redox-active scorpionate ligand ». Dalton Trans. 43, no 42 (2014) : 16066–73. http://dx.doi.org/10.1039/c4dt02331e.

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Dias, H. V. Rasika, Simone Alidori, Giancarlo Gioia Lobbia, Grazia Papini, Maura Pellei et Carlo Santini. « Small Scorpionate Ligands : Silver(I)-Organophosphane Complexes of 5-CF3-Substituted Scorpionate Ligand Combining a B−H···Ag Coordination Motif ». Inorganic Chemistry 46, no 23 (novembre 2007) : 9708–14. http://dx.doi.org/10.1021/ic701041k.

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Zhang, Fan, Thorsten Morawitz, Susanne Bieller, Michael Bolte, Hans-Wolfram Lerner et Matthias Wagner. « Metallomacrocycles from ditopic chiral scorpionate ligands ». Dalton Transactions, no 40 (2007) : 4594. http://dx.doi.org/10.1039/b707807b.

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Thomas, Jarrod R., et Scott A. Sulway. « In situ tracking and characterisation of scorpionate ligands via11B-NMR spectroscopy ». RSC Advances 11, no 27 (2021) : 16158–60. http://dx.doi.org/10.1039/d0ra10826j.

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Olyshevets, Iryna, Vladimir Ovchynnikov, Nataliia Kariaka, Viktoriya Dyakonenko, Svitlana Shishkina, Tatiana Sliva, Małgorzata Ostrowska, Aleksandra Jedyńczuk, Elżbieta Gumienna-Kontecka et Vladimir Amirkhanov. « Lanthanide complexes based on a new bis-chelating carbacylamidophosphate (CAPh) scorpionate-like ligand ». RSC Advances 10, no 42 (2020) : 24808–16. http://dx.doi.org/10.1039/d0ra04714g.

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Manna, Fabio, Mariangela Oggianu, Valentina Mameli, Stefano Lai, Angelica Simbula, Francesco Quochi, Narcis Avarvari et Maria Laura Mercuri. « Thiophenyl Anilato-Based NIR-Emitting Lanthanide (LnIII = Er, Yb) Dinuclear Complexes ». Molecules 29, no 23 (9 décembre 2024) : 5804. https://doi.org/10.3390/molecules29235804.

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By combining ErIII and YbIII ions with 3,6-dithiophene-anilate (Th2An) and scorpionate hydrotris(pyrazol-1-yl)borate (HBpz3−) ligands new luminescent dinuclear complexes are obtained. The two materials formulated as [((HB(pz)3)2Yb)2(μ-th2An)]·4DCM·1.3H2O 1Yb and [((HB(pz)3)2Er)2(μ-th2An)]·4DCM·1.8H2O 1Er, respectively, have been structurally characterized by SC-XRD and PXRD studies. This study presents a comprehensive investigation of the photophysical properties of the Th2An ligand for the first time. Our findings reveal the crucial role of the thiophene anilate as an effective optical antenna, which sensitizes near-infrared (NIR)-emitting lanthanide ions, specifically ErIII and YbIII. The significant impact of vibrational quenching on the LnIII NIR emission efficiency has been also highlighted.
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Tretiakov, Serhii, Johannes A. M. Damen, Martin Lutz et Marc-Etienne Moret. « A dianionic C3-symmetric scorpionate : synthesis and coordination chemistry ». Dalton Transactions 49, no 39 (2020) : 13549–56. http://dx.doi.org/10.1039/d0dt02601h.

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Bussey, Katherine A., Annie R. Cavalier, Jennifer R. Connell, Margaret E. Mraz, Kayode D. Oshin, Tomislav Pintauer, Danielle L. Gray et Sean Parkin. « Crystal structure of orthorhombic {bis[(pyridin-2-yl)methyl](3,5,5,5-tetrachloropentyl)amine-κ3N,N′,N′′}chloridocopper(II) perchlorate ». Acta Crystallographica Section E Crystallographic Communications 71, no 7 (27 juin 2015) : 847–51. http://dx.doi.org/10.1107/s2056989015011792.

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In the title compound, [CuCl(C17H19Cl4N3)]ClO4, the CuIIion adopts a distorted square-planar geometry defined by one chloride ligand and the three nitrogen atoms from the bis[(pyridin-2-yl)methyl](3,5,5,5-tetrachloropentyl)amine ligand. The perchlorate counter-ion is disordered over three sets of sites with refined occupancies 0.0634 (17), 0.221 (16) and 0.145 (7). In addition, the hetero-scorpionate arm of the bis[(pyridin-2-yl)methyl](3,5,5,5-tetrachloropentyl)amine ligand is disordered over two sets of sites with refined occupancies 0.839 (2) and 0.161 (2). In the crystal, weak Cu...Cl interactions between symmetry-related molecules create a dimerization with a chloride occupying the apical position of the square-pyramidal geometry typical of many copper(II) chloride hetero-scorpionate complexes.
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Da Costa, Rosenildo Correa, Benjamin W. Rawe, Nikolaos Tsoureas, Mairi F. Haddow, Hazel A. Sparkes, Graham J. Tizzard, Simon J. Coles et Gareth R. Owen. « Preparation and reactivity of rhodium and iridium complexes containing a methylborohydride based unit supported by two 7-azaindolyl heterocycles ». Dalton Transactions 47, no 32 (2018) : 11047–57. http://dx.doi.org/10.1039/c8dt02311e.

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Dyson, Gavin, Alexander Zech, Benjamin W. Rawe, Mairi F. Haddow, Alexander Hamilton et Gareth R. Owen. « Scorpionate Ligands Based on 2-Mercaptopyridine : A Ligand with a Greater Propensity To Sting ? » Organometallics 30, no 21 (14 novembre 2011) : 5844–50. http://dx.doi.org/10.1021/om200694r.

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Matveeva, Anna G., Anna V. Vologzhanina, Evgenii I. Goryunov, Rinat R. Aysin, Margarita P. Pasechnik, Sergey V. Matveev, Ivan A. Godovikov, Alfiya M. Safiulina et Valery K. Brel. « Extraction and coordination studies of a carbonyl–phosphine oxide scorpionate ligand with uranyl and lanthanide(iii) nitrates : structural, spectroscopic and DFT characterization of the complexes ». Dalton Transactions 45, no 12 (2016) : 5162–79. http://dx.doi.org/10.1039/c5dt04963f.

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Fujisawa, Kiyoshi, Masaya Shimizu et Robert K. Szilagyi. « Comparison of thallium(I) complexes with mesityl-substituted tris(pyrazolyl)hydroborate ligands, [Tl{HB(3-Ms-5-Mepz)3}] and [Tl{HB(3-Ms-5-Mepz)2(3-Me-5-Mspz)}] ». Acta Crystallographica Section C Structural Chemistry 72, no 11 (5 octobre 2016) : 786–90. http://dx.doi.org/10.1107/s2053229615023797.

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Tris(pyrazolyl)borate (scorpionate) ligands can be considered as the most prolific ligands in contemporary coordination chemistry due to the availability of various steric and electronic substituents at the pyrazolyl rings that allow fine-tuning of the open-coordination site for metal centres. The thallium(I) complexes of anionic tridentate-chelating scorpionate ligands, namely [tris(3-mesityl-5-methyl-1H-pyrazol-1-yl-κN2)hydroborato]thallium(I) monohydrate, [Tl(C39H46BN6)]·H2O, (I), and [bis(3-mesityl-5-methyl-1H-pyrazol-1-yl-κN2)(5-mesityl-3-methyl-1H-pyrazol-1-yl-κN2)hydroborato]thallium(I), [Tl(C39H46BN6)], (II), show a {TlIN3} coordination, with average TlI—N bond lengths of 2.53 and 2.55 Å in (I) and (II), respectively. The overall TlIcoordination geometry is distorted trigonal pyramidal, with the average N—TlI—N angle being approximately 73° for both. The dihedral angle between the planes of the pyrazolyl and benzene rings of the mesityl group is 82° in (I), while the corresponding angles in (II) are in the range 64–104°. The structural differences between the two ligands are expected to contribute to the different reactivities of the transition metal coordination complexes towards activation of small molecules such as dioxygen and ethylene.
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Colmer, Hannah E., Robert A. Geiger, Domenick F. Leto, Gayan B. Wijeratne, Victor W. Day et Timothy A. Jackson. « Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand ». Dalton Trans. 43, no 48 (2014) : 17949–63. http://dx.doi.org/10.1039/c4dt02483d.

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A peroxomanganese(iii) species with a scorpionate (Tp) ligand is characterized by X-ray crystallography, electron paramagnetic resonance, and magnetic circular dichroism spectroscopy, revealing a distinct electronic structure.
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Naktode, Kishor, Th Dhileep N. Reddy, Hari Pada Nayek, Bhabani S. Mallik et Tarun K. Panda. « Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine ». RSC Advances 5, no 63 (2015) : 51413–20. http://dx.doi.org/10.1039/c5ra04696c.

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Synthetic and structural details of flexible scorpionate ligand based on 2-mercaptopyridine (Bmp) supported heavier alkaline earth metal complexes with metal–sulfur bonds (metal = Sr, Ba) have been presented.
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