New dodecanuclear phenylphosphonate-bridged Co(II) complexes

Burkovskaya, N. P.; Никифорова, М. Е.; Кискин, М. А.; Lermontov, A. S.; Bogomyakov, A. S.; Mironov, V. S.; Dobrokhotova, Zhanna V.; Pekhnyo, V. I.; Сидоров, А. А.; Новоторцев, В. М.; Еременко, И. Л.

doi:10.1016/j.poly.2011.08.039

Cited by 11 publications

(8 citation statements)

References 36 publications

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“…Perhaps, that is why phos phonate clusters I and III-VI contain no internal phosphorus atoms and the geometry of the metal core differs from that observed in the polyoxometallate anions [33]. This does not principally impede the fur ther growing of the metal framework of the phospho nate clusters, which was shown for the cobalt(II) com plexes [26].…”

Section: Resultsmentioning

confidence: 95%

“…The structure of the metallohydroxophosphonatecarboxylate framework of molecule I is close to that of compound [(μ L) 6 Ni 12 (μ 3 OH) 4 (μ 6 O 3 PPh) 4 (μ Piv) 12 ] (III)) obtained earlier by the solvothermal method under pressure at 150°C, where L are disor dered molecules HPiv, HOAc, and H 2 O [16], and to a series of the synthesized cobalt(II) complexes [(μ L) 6 Co 12 (μ 3 OH) 4 (μ 6 O 3 PPh) 4 (μ Piv) 12 ] (L = Hmhp (IV), THF (V) or THF and HPiv (VI)) [26]. − PhPO bonds are considerably longer than Ni-О(μ Piv) and Ni-О(μ 3 OH) ( Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…As shown in earlier works on the synthesis of the phosphonate complexes, the additional use of Hmhp considerably extends possibilities of the synthesis of compounds with higher nuclearity [26,27]. However, the data on the influence of the nature of metal centers and additional ligands and their geometric parameters and synthesis conditions on the geometry of the poly nuclear metal phosphonates are rather restricted and, therefore, they require more detailed investigation.…”

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New nickel(II) carboxylate-phosphonate cluster: Synthesis and structure

et al. 2012

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Among many polynuclear phosphonate complexes of transition metals, the so called mixed ligand com plexes play a special role. The use of additional ligands in the synthesis of polynuclear architecture makes it possible to solve the problem of a low solubility of the phosphonate complexes and, finally, to obtain the polynuclear architecture with a specified set of physi cochemical properties. This class of compounds attracts attention of researchers due to their ability to ion exchange, adsorption, and proton conductivity. This assumes their potential use in photochemistry, electrooptics, and catalysis. In addition, the possibility of using such molecules in sensor devices and as molecular precursors for the preparation of various materials cannot be excluded [1][2][3][4][5][6][7][8][9].The method of self assembling can be distin guished among the methods for the preparation of such homo and heteronuclear molecules. In this method, the heteroligand coordination sphere is formed by phosphonate bridges and, for example, car boxylate anions [10][11][12][13][14][15][16][17][18][19] or other organic ligands of the type of 2 hydroxypyridine derivatives [20][21][22][23].In this work, we used trimethylacetate ligands determining, as a rule, the high spin state of metal atoms in transition metal complexes and containing bulky tert butyl substituents that provide the forma tion of the insular structure with high solubility in organic media. It could be assumed that the use of metal containing fragments with the high spin metal ions in molecular self assembling of a polynuclear structure with phosphonate bridges would result in the formation of a magnetically active architecture, because the presence of unpaired electrons on each metal center induces, as a rule, spin-spin exchange interactions between the adjacent metal ions and the appearance of antiferro , ferri , or ferromagnetic properties [10, 15, 17-19, 24, 25].As shown in earlier works on the synthesis of the phosphonate complexes, the additional use of Hmhp considerably extends possibilities of the synthesis of compounds with higher nuclearity [26,27]. However, the data on the influence of the nature of metal centers and additional ligands and their geometric parameters and synthesis conditions on the geometry of the poly nuclear metal phosphonates are rather restricted and, therefore, they require more detailed investigation.The results on chemical assembling of the polynu clear mixed ligand Ni(II) complexes are presented in this work. EXPERIMENTALComplex I was synthesized in air using commer cially available solvents MeCN and THF. Phenylphos phonic acid (Aldrich), pivalic acid (Aldrich), Hmhp (Fluka), and KOH (analytical grade) were used for the synthesis. Phenylphosphonic acid potassium salt K 2 O 3 PPh was obtained by the reaction of KOH and Н 2 O 3 PPh. Nickel pivalate [Ni 9 (OH) 6 (Piv) 12 (HPiv) 4 ] (II) was synthesized according to a described proce dure [28].Synthesis of [(μ 2 Hmhp) 6 Ni 12 (µ 3 OH) 4 (µ 6 O 3 PPh) 4 (μ 2 Piv) 12 ] · 7.5MeCN ⋅ 1.5THF (I ⋅ 7....

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

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New nickel(II) carboxylate-phosphonate cluster: Synthesis and structure

et al. 2012

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“…6 The phosphonate dianion RPO 3 2− has a promising structure capable to form units for the self-assembly of polynuclear complexes. 7 Polynuclear transition metal phosphonates have attracted attention because of their ion-exchange and adsorption ability and their proton conductivity, which makes these compounds useful in photochemistry, electro-optics, and catalysis. Several transition metal phenylphosphonates were prepared.…”

Section: Introductionmentioning

confidence: 99%

“…Several transition metal phenylphosphonates were prepared. 1,[8][9][10][11][12] Burkovskaya et al 7 reported the X-ray structure of decanuclear phenylphosphonate bridged Co(II) complexes. Furthermore, Wang et al 8 reported a single chain cobalt phenylphosphonate complex [Co(phen)(4,4 -bpy)(C 6 H 5 PO 3 H) 2 ] n 0.5 H 2 O (phen=1,10-phenanthroline, 4,4 -bpy=4,4 -bipyridine).…”

Section: Introductionmentioning

confidence: 99%

Evidences for Chelating Complexes of Lithium with Phenylphosphinic and Phenylphosphonic Acids: A Spectroscopic and DFT Study

Sunjuk

El‐Eswed

Dawoud

et al. 2014

Phosphorus, Sulfur, and Silicon and the Related Elements

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Lithium complexes were prepared with phenylphosphinic and phenylphosphonic acids. The complexes were studied in the solid state using Fourier transform infrared spectroscopy spectroscopy and in solution (methanol) using 1 H, 13 C, and 31 P Nuclear magnetic resonance spectroscopy (NMR) spectroscopy; the most preferred structures of the complexes were determined by density functional theory (DFT) computational method. Although methanol has a strong solvation effect on lithium ions and ligands, which causes dissociation of the complexes, significant changes of the NMR spectra of the complexes (relative to those of the free ligands) were observed. The new spectroscopic results indicate the presence of the phenylphosphinic acid tautomer (I: C 6 H 5 PH( O)OH) rather than that of phenyl-phosphorous acid (II: C 6 H 5 P(OH) 2 ) in deuterated methanol showing PH/PD exchange. On the other hand, tautomer I predominates in the complex with lithium without showing PH/PD exchange. The DFT PREPARATION OF LITHIUM COMPLEXES WITH PHENYLPHOSPHINIC 559calculations predict that tautomer I is the preferred structure in the case of free ligand and lithium complex. The absence of a PH/PD exchange in the complex is due to the formation of a chelating complex, rather than of a simple salt between lithium ion and the two oxygen atoms of I, which prevent tautomerization of I into II. DFT calculations support the formation of lithium chelating complexes. The lithium ion was found to affect the spectroscopic properties of phenylphosphinic acid more dramatically than those of phenylphosphonic acid.

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