Anhydrous Nitrates and Nitrosonium Nitratometallates of Manganese and Cobalt, M(NO3)2, NO[Mn(NO3)3], and (NO)2[Co(NO3)4]: Synthesis and Crystal Structure

Tikhomirov, Grigory; Znamenkov, Konstantin O.; Morozov, Igor; Kemnitz, Erhard; Troyanov, S. I.

doi:10.1002/1521-3749(200201)628:1<269::aid-zaac269>3.0.co;2-p

Cited by 25 publications

(22 citation statements)

References 10 publications

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“…However, it is known that crystalline N 2 O 5 consists of nitronium and nitrate ions with six N···O contacts of 2.724 Å [28], but its sublimation occurs in form of N 2 O 5 molecules. Volatility of both neutral complexes, Fe(NO 3 ) 3 and Zr(NO 3 ) 4 , is well documented in [10] and [7], respectively. Therefore, it is more probable that the sublimation mechanism of M(NO 3 ) n ·N 2 O 5 complexes includes an independent sublimation of N 2 O 5 and M(NO 3 ) n with their subsequent recombination.…”

Section: Resultsmentioning

confidence: 99%

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New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Tikhomirov¹,

Morozov²,

Znamenkov³

et al. 2002

Z. anorg. allg. Chem.

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Crystalline NO 2 [Fe(NO 3 ) 4 ] was obtained by dehydration of a solution of Fe(NO 3 ) 3 in 100 % HNO 3 and subsequent sublimation. NO 2 [Zr(NO 3 ) 5 ] was synthesized by reaction of ZrCl 4 with N 2 O 5 followed by sublimation in vacuum. X-ray single crystal structure determination showed both compounds to consist of nitronium cations, NO 2 ϩ , and nitratometalate anions. N-O distances in the linear NO 2 ϩ cations are in the range of 1.08Ϫ1.13 Å . In both [Fe(NO 3 ) 4 ] Ϫ and [Zr(NO 3 ) 5 ] Ϫ anions, all nitrate groups are coordinated bidentately with average M-O distances 2.134 and Neue Flüchtige Nitrylnitratometallate: NO 2 [Fe(NO 3 ) 4 ] und NO 2 [Zr(NO 3 ) 5 ] ؊ Synthese und Kristallstruktur Inhaltsübersicht. Kristallines NO 2 [Fe(NO 3 ) 4 ] wurde durch Einengen einer Lösung von Fe(NO 3 ) 3 in 100%iger HNO 3 und nachfolgender Sublimation des erhaltenen Feststoffes hergestellt. NO 2 [Zr(NO 3 ) 5 ] wurde durch Reaktion von ZrCl 4 mit N 2 O 5 und anschließender Vakuumsublimation synthetisiert. Die Röntgenein-kristallstrukturanalyse zeigt, dass beide Verbindungen aus Nitrylkationen, NO 2 ϩ , und Nitratometallatanionen bestehen. Die N-OAbstände in den linearen NO 2 ϩ -Kationen liegen im Bereich von 1.08Ϫ1.13 Å . In den [Fe(NO 3 ) 4 ] Ϫ -und [Zr(NO 3 ) 5 ] Ϫ -Anionen sind

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Section: Resultsmentioning

confidence: 99%

“…However, many nitronium nitratometalates are able to sublime at relatively low temperature without composition change. In the present work, we have 4 ], was collected on a cool finger at 15°C. It is pale brown in thin layer and almost black in thick one with purple blink in reflected light.…”

Section: Introductionmentioning

confidence: 99%

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Tikhomirov¹,

Morozov²,

Znamenkov³

et al. 2002

Z. anorg. allg. Chem.

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“…The presence of sulfuric acid as the drying agent does not exclude the possibility of the forma tion of nitrate hydrates. 11 The possibility of crystallization from a nitric solution of nitronium derivatives was con firmed in the study, 12 5 ] salts, 5 the N-O distances in the nitronium cations vary from 1.08 to 1.13 Å (aver., 1.11 Å). Each nitronium cation is surrounded by three nitrate an ions in such a way that the nitrogen atoms of the cations and anions are in a single plane, whereas the O(5) atoms The structure of complex 1 was confirmed by the IR spectrum, which shows vibrations at 570 cm -1 belonging to the NO 2 + cation and a characteristic broad absorption band at 3500 cm -1 assigned to H 2 O molecules.…”

Section: Resultsmentioning

confidence: 99%

“…4 The sublimate can contain crystals of nitronium pentanitratozirconate (NO 2 )[Zr(NO 3 ) 5 ]. The latter is the only zirconium(IV) nitrate complex whose crystal structure has been unambiguously established.…”

mentioning

confidence: 99%

“…In this compound, the Zr IV atom is bound to five bidentate nitrate groups and has a coordination num ber of 10, which has not been observed earlier for zir conium. 5 The sublimate prepared according to an analo gous procedure was recrystallized from nitroethane. This made it possible to isolate crystals whose composi tions were detertmined by Raman spectroscopy and X ray diffraction: 6 (NO) 3 …”

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Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

et al. 2005

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The zirconium nitrate complexes (NO 2 )[Zr(NO 3 ) 3 (H 2 O) 3 ] 2 (NO 3 ) 3 (1), Cs [Zr(NO 3 ) 5 ] (2), (NH 4 ) [Zr(NO 3 ) 5 ](HNO 3 ) (3), and (NO 2 ) 0.23 (NO) 0.77 [Zr(NO 3 ) 5 ] (4) were prepared by crys tallization from nitric acid solutions in the presence of H 2 SO 4 or P 2 O 5 . The complexes were characterized by X ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO 3 ) 3 (H 2 O) 3 ] + complex cations in which the Zr IV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the Zr IV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO 3 ) 5 ] -anions and Cs + or NH 4 + cations, respectively. In addition, com plex 3 contains HNO 3 molecules. Complex 4 differs from (NO 2 )[Zr(NO 3 ) 5 ] in that three fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO + , resulting in a decrease in the unit cell parameters. In the [Zr(NO 3 ) 5 ] -anion involved in complexes 2-4, the Zr IV atom is coordinated by five bidentate nitrate groups and has an unusually high coordina tion number of 10. The coordination polyhedron is a bicapped square antiprism.Until recently, only a few zirconium(IV) nitrate com plexes were known, which is associated with the fact that these complexes are highly prone to hydrolysis giving rise to zirconyl derivatives. For example, zirconyl nitrate hy drate ZrO(NO 3 ) 2 •2H 2 O generally crystallizes from nitric acid solutions. The crystal structure of this compound consists of the infinite OH bridged [Zr(NO 3 ) 2 (OH) 2 ] n chains, which are linked to each other through crystalli zation water molecules. 1 Crystalline precipitates, which decomposed in air to form ZrO(NO 3 ) 2 •2H 2 O, were iso lated from saturated solutions of ZrO(NO 3 ) 2 •nH 2 O (n = 2, 6) or ZrO(OH)(NO 3 )•2H 2 O in 70-100% HNO 3 . 2 In the cited study, the Zr(NO 3 ) 4 •6H 2 O and Zr(NO 3 ) 4 • •5H 2 O compositions were assigned to these precipitates, and the unit cell parameters of both compounds were determined. Evidence for the existence of the acidic salt Zr(NO 3 ) 4 •2HNO 3 •4H 2 O was reported; 3 however, the au thor pointed out a possible inaccuracy of the quantitative composition of zirconium nitrates associated with an un avoidable loss of nitric acid in the course of sampling and treatment of liquid and solid phases.The Zr(NO 3 ) 4 salt can be prepared by the reaction of ZrCl 4 with an excess amount of nitric anhydride (nitro gen pentoxide) followed by sublimation of zirco nium tetranitrate during heating of the reaction mix ture in vacuo. 4 The sublimate can contain crystals of nitronium pentanitratozirconate (NO 2 )[Zr(NO 3 ) 5 ]. The latter is the only zirconium(IV) nitrate complex whose crystal structure has been unambiguously established. In this compound, the Zr IV atom is bound to five bidentate nitrate groups and has a coordination num ber of 10, which has not been observed earlier for zir conium. 5 The sublimate prepared...

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Ethylammonium nitrate enhances the extraction of transition metal nitrates by tri‐n‐butyl phosphate (TBP)

Zhang

Onghena

et al. 2021

AIChE Journal

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Several molecular polar solvents have been used as solvents of the more polar phase in the solvent extraction (SX) of metals. However, the use of hydrophilic ionic liquids (ILs) as solvents has seldomly been explored for this application. Here, the hydrophilic IL ethylammonium nitrate (EAN), has been utilized as a polar solvent in SX of transition metal nitrates by tri-n-butyl phosphate (TBP). It was found that the extraction from EAN is considerably stronger than that from a range of molecular polar solvents. The main species of Co(II) and Fe(III) in EAN are likely [Co(NO 3) 4 ] 2− and [Fe(NO 3) 4 ] − , respectively. The extracted species are likely Fe(TBP) 3 (NO 3) 3 and a mixture of Co(TBP) 2 (NO 3) 2 and Co(TBP) 3 (NO 3) 2. The addition of H 2 O or LiCl to EAN reduces the extraction because the metal cations coordinate to water molecules and chloride ions stronger than to nitrate ions. This study highlights the potential of using hydrophilic ILs to enhance SX of metals.

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Anhydrous Nitrates and Nitrosonium Nitratometallates of Manganese and Cobalt, M(NO3)2, NO[Mn(NO3)3], and (NO)2[Co(NO3)4]: Synthesis and Crystal Structure

Cited by 25 publications

References 10 publications

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

Ethylammonium nitrate enhances the extraction of transition metal nitrates by tri‐n‐butyl phosphate (TBP)

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