Metal-Promoted Exopolyhedral Substitution of Terminal Hydrogen Atoms in the Closo-Decaborate Anion [B10H10]2– in the Presence of Copper(II): Formation of the Substituted Derivative [2-B10H9OH]2–

Малинина, Е. А.; Korolenko, Svetlana E.; Жданов, А. П.; Авдеева, В. В.; Привалов, В. И.; Кузнецов, Н. Т.

doi:10.1007/s10876-020-01840-5

Cited by 14 publications

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“…Here, we studied the reactions of gold(III) complexes [Au(L)Cl 2 ] + containing chelating N,N-ligands (L = bipy, phen) with the boron cluster anions. Earlier, it was found that iron(III) and cobalt(III) salts react with [B n H n ] 2− anions (n = 10, 12) in the presence of bipy and phen, giving metal(II) compounds [55] with the boron clusters as counterions or even with substituted derivatives of the closo-decaborate anion with OH or Phen substitutes [56,57]. In the case of less reactive [B 12 H 12 ] 2− , it was possible to isolate the cobalt(III) complex [Co(phen) 3 ][B 12 H 12 ]NO 3 [44].…”

Section: Resultsmentioning

confidence: 99%

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

et al. 2022

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Gold(III) complexation with the octadecahydrido-eicosaborate anion [B20H18]2– was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl2]BF4 (L = bipy, phen) reacted with [B20H18]2–, complexes [Au(L)Cl2]2[B20H18] were isolated. The compounds consisted of a cationic gold(III) complex [Au(L)Cl2]+ and the hydridoborate cluster as a counterion. X-ray diffraction studies revealed weak B–H...Au interactions for both compounds. Note that more reactive anions [BnHn]2– (n = 10, 12) in similar reactions with gold(III) complexes resulted in gold mirror reactions.

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Section: Resultsmentioning

confidence: 99%

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

et al. 2022

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“…), with substituted derivatives of boron cluster anions, containing the BÀ X exo-polyhedral bonds (X = N, O, S, Hal), is poorly studied, and for some of them, such as cadmium(II), is absent altogether. [17] Tris-chelate nickel(II) [NiL 3 ][2-B 10 H 9 (OH)] (L = 2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), 2,2'-bipyridylamine (bpa), and 1,2-diaminobenzene (dab)), [18] [Ni(bipy) 3 ][B 12 H 11 Cl] [19] and cobalt(II) [Co(phen) 3 ][2-B 10 H 9 (OC(H)O)] [20] complexes, binuclear [Cu 2 (bipy) 4 (μ-CO 3 )][2-B 10 H 9 (OH)] [21] and mononuclear [Cu-(bpa) 2 (CH 3 CN) 2 ][2-B 10 H 9 (bpa)] 2 , [22,23] [Cu(1,2-bis(4pyridyl)acetylene)][B 12 H 11 I] [16] copper(II) complexes containing the boron cluster anion as a counterion are described in the literature.…”

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confidence: 99%

Experimental and Theoretical Study of the Features of Zinc(II) and Cadmium(II) Complexation with the Substitutedcloso‐Hydridoborate Anion [2‐B₁₀H₉(OH)]²⁻

et al. 2023

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Herein, we studied the experimental and theoretical foundations of the process of zinc(II) and cadmium(II) complexation with 2‐hydroxido‐nonahydrido‐closo‐decaborate(2−) anion [2‐B10H9(OH)]2− in the presence of azaheterocyclic ligands L (L=2,2′‐bipyridyl (bipy), 1,10‐phenanthroline (phen), and 2,2′‐bipyridylamine (bpa)), which can be used as model system for obtaining complexes with the required composition and structure. The first examples of mixed‐ligand Zn(II) and Cd(II) complexes with [2‐B10H9(OH)]2− coordinated by the metal atom were isolated selectively. The structures of zinc(II) complexes [Zn(bipy)2(2‐B10H9(OH)‐κ2H1,O)] ⋅ 2CH3CN (1 ⋅ 2CH3CN) and [Zn(phen)2(2‐B10H9(OH)‐κ2H9,O)] ⋅ 2CH3CN (2 ⋅ 2CH3CN), as well as two cadmium(II) bond isomers [Cd(bipy)2(2‐B10H9(OH)‐κ2H1,O)] (4 a) and [Cd(bipy)2(2‐B10H9(OH)‐κ2H9,H10)] (4 b) bound into a dimeric pair in the complex [Cd(bipy)2(2‐B10H9(OH))] (4), and cadmium(II) complex [Cd(bpa)2(2‐B10H9(OH)‐κ2H7,H10)] (7) were solved by single‐crystal X‐ray diffraction (XRD). Density functional theory (DFT) calculations show that for cadmium(II) the formation of both multicenter BH−Cd−HB and BO(H)−Cd−HB bonds is equally probable. The affinity of zinc(II) for oxygen leads to preferential formation of complexes via BO(H)−Zn−HB bonds than BH−Zn−HB bonds. The M−B(H) bonding was found to be presumably electrostatic in nature, which could be the reason of topological isomerism of zinc(II) and cadmium(II) decaborates.

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“…Boron cluster anions possess three-dimensional aromaticity and have delocalized electron density [14,15], which makes it possible to replace terminal hydrogen atoms with various functional groups [16][17][18][19][20]. Substituted derivatives of boron cluster anions are also capable of forming complexes with metal atoms, acting as ligands of the inner sphere (due to the coordination of B-H groups by the metal atom or due to the coordination of the functional group of the introduced substituent) or as counterions [21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Spontaneous Isomerization [trans-B20H18]2– → [iso-B20H18]2– during Cobalt(II) Complexation with Phenanthroline

Авдеева

Кубасов

Korolenko

et al. 2022

Russ. J. Inorg. Chem.

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In this work, the cobalt(II) complexation with 1,10-phenanthroline (Phen) in the presence of the [trans-B20H18]2– anion has been studied. At a Co : Phen = 1 : 2 ratio in acetonitrile, a binuclear cobalt(II) complex with bridging chlorine atoms and the boron cluster anion as a counterion [(Phen)2Co(µ-Cl)2Co(Phen)2][trans-B20H18] has been isolated. However, during slow crystallization (within a month), spontaneous isomerization of [trans-B20H18]2– into [iso-B20H18]2– is observed. It has been established by X-ray diffraction analysis that in the crystal of the final compound [(Phen)2Co(µ-Cl)2Co(Phen)2][trans-B20H18]1/3[iso-B20H18]2/3, co-crystallization of both isomeric forms of the octadecahydroeicosaborate anion is observed for the first time. The presence of the iso form of the boron cluster anion is also confirmed by IR spectroscopy data: the spectrum of the product shows a band of stretching vibrations of the BHB bridge groups at 1773 cm–1, which is absent in the trans-form of the boron cluster.

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Metal-Promoted Exopolyhedral Substitution of Terminal Hydrogen Atoms in the Closo-Decaborate Anion [B10H10]2– in the Presence of Copper(II): Formation of the Substituted Derivative [2-B10H9OH]2–

Cited by 14 publications

References 41 publications

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

Experimental and Theoretical Study of the Features of Zinc(II) and Cadmium(II) Complexation with the Substitutedcloso‐Hydridoborate Anion [2‐B₁₀H₉(OH)]²⁻

Spontaneous Isomerization [trans-B20H18]2– → [iso-B20H18]2– during Cobalt(II) Complexation with Phenanthroline

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Metal-Promoted Exopolyhedral Substitution of Terminal Hydrogen Atoms in the Closo-Decaborate Anion [B10H10]2– in the Presence of Copper(II): Formation of the Substituted Derivative [2-B10H9OH]2–

Cited by 14 publications

References 41 publications

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

Experimental and Theoretical Study of the Features of Zinc(II) and Cadmium(II) Complexation with the Substitutedcloso‐Hydridoborate Anion [2‐B10H9(OH)]2−

Spontaneous Isomerization [trans-B20H18]2– → [iso-B20H18]2– during Cobalt(II) Complexation with Phenanthroline

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Experimental and Theoretical Study of the Features of Zinc(II) and Cadmium(II) Complexation with the Substitutedcloso‐Hydridoborate Anion [2‐B₁₀H₉(OH)]²⁻