Nickel(II) complexes with nitrogen-containing derivatives of the closo-decaborate anion

Кубасов, А. С.; Matveev, E. Yu.; Ретивов, В. М.; Akimov, S. S.; Razgonyaeva, G. A.; Polyakova, I. N.; Votinova, N. A.; Zhizhin, K. Yu.; Кузнецов, Н. Т.

doi:10.1007/s11172-014-0412-2

Cited by 36 publications

(5 citation statements)

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“…In addition, the amidoxime derivatives generate 3-substituted 5-ethyl-1,2,4-oxadiazoles detected in trace amounts by HRESI + -MS (f); the latter reaction between nitriles and amidoximes has been studied 21 by us earlier. Hydroxyguanidine derivatives (Ph 3 PCH 2 Ph)[1], (Ph 3 PCH 2 Ph) [4], (Ph 3 PCH 2 Ph) [9], and (Ph 3 PCH 2 Ph) [12] decompose in solutions at RT for approximately 2 weeks, giving a broad mixture of products, whereas aromatic ketoxime derivative (Ph 3 PCH 2 Ph) [8] in solutions at RT decomposes after 4 days. In the cases of (Ph 3 PCH 2 Ph)[2−3], (Ph 3 P-CH 2 Ph)[5−7], (Ph 3 PCH 2 Ph)[10−11], and (Ph 3 PCH 2 Ph)- [13−14], the hydrolysis in a MeOH/H 2 O (10/1, v/v) mixture completes after 4 h at 60 °C.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Reactions of the first type proceed via redox destruction of the cluster moiety and include either reduction to the nido -decaborane [B 10 H 14 ] or 6-substituted nido -boranes [B 10 H 13 X] (X = OH, F, Cl, Br, I), or oxidative coupling leading to [B 20 H 18 ] 4– . The second type of reactions does not affect the cluster unit but includes substitution of one or two hydrides by NR 3 , OH (water and OH – ), OR and OR 2 , MeCO 2 , phen, NCO, CO, and also by RCN . When the closo -decaborates are functionalized with a nitrile group, they could be easily derivatized further by nucleophilic addition to the nitrile C atom.…”

Section: Introductionmentioning

confidence: 99%

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Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

et al. 2016

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Three types of oxime species, i.e., 4-morpholylcarbamidoxime (hydroxyguanidine), phenylacetamidoxime and benzamidoxime (amidoximes), and cyclohexanone oxime and benzophenone oxime (ketoximes), react at room temperature with the 2-nitrilium closo-decaborate clusters, leading to 2-iminium closo-decaborates (14 examples; 57–94%). These species were characterized by ICPMS-based boron elemental analysis, HRESI–-MS, molar conductivity, IR, 1H{11B}, and 11B{1H} NMR spectroscopies, and additionally by single-crystal X-ray diffraction (for six compounds). On the basis of kinetic data, ΔH ⧧, ΔS ⧧, and ΔG ⧧ of the additions were determined, showing a 4 order-of-magnitude decrease in reactivity from the hydroxyguanidine to the aromatic ketoxime as entering nucleophiles. The results of DFT calculations indicate that the mechanism for these reactions is stepwise and is realized through the formation of the orientation complex of the nitrone form, R2R3CN+(H)O–, of oximes with [B10H9NCEt]−, giving further an acyclic intermediate (the rate-determining step), followed by proton migration, leading to the addition product. The calculated overall activation barrier for these transformations is consistent with the experimental kinetic observations. This work provides, for the first time, a broad nucleophilicity series of oximes, which is useful to control various nucleophilic additions of oxime species.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

et al. 2016

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“…Particularly, reactions of the 1,4-dioxane derivative of the [B 10 H 10 ] 2anion with ethylenediamine in ethanol lead to the formation of the derivative of the closo-decaborate anion 2-B 10 H 9 O(CH 2 ) 2 O(CH 2 ) 2 NH(CH 2 ) 2 NH 2 )] 2− with pendant ethylenediamine (en) group separated from the boron cluster by an alkoxy spacer. This anion was used in nickel(II) complexation [82]. In the compounds obtained, the metal atom coordinates only the substituent introduced into the boron cluster, whereas all BH groups remain uncoordinated.…”

Section: Opening Of the Cyclic Substituentmentioning

confidence: 99%

Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)

et al. 2022

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This review systematizes data on the coordination ability of mono- and disubstituted derivatives of boron cluster anions and carboranes in complexation with transition metals. Boron clusters anions [BnHn]2–, monocarborane anions [CBnHn–1]–, and dicarboranes [C2BnHn–2] (with non-functionalized carbon atoms) (n = 10, 12) containing the B–X exo-polyhedral bonds (X = N, O, S, Hal) are discussed. Synthesis and structural features of complexes known to date are described. The effect of complexing metal and substituent attached to the boron cage on the composition and structures of the final complexes is analyzed. It has been established that substituted derivatives of boron cluster anions and carboranes can act as both ligands and counterions. A complexing agent can coordinate substituted derivatives of the boron cluster anions due to three-center two-electron 3c2e MHB bonds, by the substituent functional groups, or a mixed type of coordination can be realized, through the BH groups of the boron cage and the substituent. As for B-substituted carboranes, complexes with coordinated substituents or salts with non-coordinated carborane derivatives have been isolated; compounds with MHB bonding are not characteristic of carboranes.

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“…Several transition metals complexes with the cluster anion coordinated only by a functional substituent are known. Among them, two nickel(II) complexes [Ni(ethylenediamine)(2-B 10 H 9 (O-(CH 2 ) 2 O(CH 2 ) 2 NH(CH 2 ) 2 NH 2 )))] [24] and [Na 6 (THF) 15 ][Ni-(B 12 H 11 (NH 2 ))] 4 , [25] phthalocyanine zinc(II) and cobalt(II) complexes, [26][27][28] and ruthenium(II) complex [Ru-(Ph 3 P) 3 H 2 (N 2 B 10 H 8 (S(CH 3 ) 2 ))] [29] can be noted. Note that, the BH groups of the cluster are not directly involved in the formation of the metal coordination polyhedron in these complexes.…”

Section: Introductionmentioning

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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Nickel(II) complexes with nitrogen-containing derivatives of the closo-decaborate anion

Cited by 36 publications

References 14 publications

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)

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

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Nickel(II) complexes with nitrogen-containing derivatives of the closo-decaborate anion

Cited by 36 publications

References 14 publications

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

Nucleophilicity of Oximes Based upon Addition to a Nitrilium closo-Decaborate Cluster

Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)

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

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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⁻