ChemInform Abstract: Synthesis and Structure of Polynuclear Peroxofluorozirconates K6Zr3F12(O2)3·2 H2O2·2 H2O.

Chernyshov, B. N.; Диденко, Н. А.; Буквецкий, Б. В.; Герасименко, А. В.; Kavun, V. Ya.; Sergienko, S. S.

doi:10.1002/chin.199005030

Cited by 2 publications

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“…The presence of one tridentate and four bidentate ligands in the inner sphere creates a rare 11-coordinate environment around the thorium(IV) centers that are best described as augmented sphenocorona. A similar [M 3 (O 2 ) 3 ] core has been observed in several zirconium(IV) fluorides as well as in {Zr[MeC(N i Pr) 2 ] 2 (O 2 )} 3 . , In the latter compound, it was established that the reduction of O 2 to O 2 2– is ligand-based and appropriate ligand decomposition products are observed. However, this cluster is unstable in solution and ultimately decomposes to dimeric and polymeric oxo species via degradation of the peroxide anions.…”

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confidence: 65%

Understanding the Scarcity of Thorium Peroxide Clusters

et al. 2017

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The reaction of Th(NO)·5HO with 3 equiv of 2,2',6',2″-terpyridine (terpy) in a mixture of acetonitrile and methanol results in formation of the trinuclear thorium peroxide cluster [Th(O)(terpy)(NO)]. This cluster is assembled via bridging by μ-η:η peroxide anions between thorium centers. It decomposes upon removal from the mother liquor to yield Th(terpy)(NO) and Th(terpy)(NO)(EtOH). The peroxide formation appears to be radiolytic in origin and is, most likely, generated from radiolysis of water by short-lived daughters generated from Th decay. This cluster does not form when freshly recrystallized Th(NO)·5HO is used as the starting material and requires an aged source of thorium. Analysis of the bonding in these clusters shows that, unlike uranium(VI) peroxide interactions, thorium(IV) complexation by peroxide is quite weak and largely ionic. This explains its much lower stability, which is more comparable to that observed in similar zirconium(IV) peroxide clusters.

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confidence: 65%

Understanding the Scarcity of Thorium Peroxide Clusters

et al. 2017

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“…25 There is a Zr peroxo fluoro trimer, where one bridging peroxo group between the metal centers results in a 3.903 Å Zr−Zr distance. 19 On the other hand, a μ 4 connection has been previously observed in [M 2 (O 2 ) 2 ] dimer units for both Zr 49,50 and Hf. 51 These dimer units were stabilized by bulky organic ligands or lacunary polyoxometalate ligands.…”

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confidence: 90%

“…For comparison, there have been a few multinuclear peroxo compounds of Zr reported . There is a Zr peroxo fluoro trimer, where one bridging peroxo group between the metal centers results in a 3.903 Å Zr–Zr distance . On the other hand, a μ 4 connection has been previously observed in [M 2 (O 2 ) 2 ] dimer units for both Zr , and Hf .…”

Section: Resultsmentioning

confidence: 99%

“…Zr/Hf peroxide complexation in solution is of special relevance to all of the lithography steps. Few zirconium peroxo salts and complexes have been reported − and even fewer for Hf . More recently, we and others have shown that peroxide enables the creation of multinuclear metal oxo/peroxo motifs, such as the peroxide-bridged Hf 6 and Zr 25 ring clusters and an oxo-centered Zr tetrahedron. − Isolation of such polynuclear compounds is challenged by the spontaneous hydrolysis/condensation of acidic Zr/Hf, leading to self-assembly of the ubiquitous [M 4 (OH) 8 (H 2 O) 12 ] 8+ square tetramer, M 4 . , In fact, M 4 is the starting point for the most Zr/Hf aqueous reactions.…”

Section: Introductionmentioning

confidence: 99%

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Countercation-Controlled Nuclearity of Zr/Hf Peroxo Oxalates

Kozma

Zakharov

Nyman

2020

Crystal Growth & Design

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Understanding fundamental differences between zirconium and hafnium chemistry contributes to our fundamental understanding of the periodic table and leads to devising necessary separations for high-precision nuclear and microelectronics applications, developing water-based nanolithographic processes, and creating new robust metal−organic frameworks for catalysis and separations. Here we crystallize a rich matrix of polynuclear Zr and Hf species differentiating in complexation with peroxide and oxalate in mild acid, where the countercations influence polymerization. Hf only complexes oxalate, yielding polymericNa 6 [Hf 2 (OH) 2 (C 2 O 4 ) 6 ], and Li 2 K 4 [Hf 2 (OH) 2 (C 2 O 4 ) 6 ] and mononuclear K 4 Hf(C 2 O 4 ) 4 , Rb 4 Hf(C 2 O 4 ) 4 , and Cs 4 Hf-(C 2 O 4 ) 4 . Zr complexes both peroxide and oxalate to yield the ring structures (N-( C H 3 ) 4 ) 6 [ Z r 6 ( O 2 ) 6 ( O H ) 6 ( C 2 O 4 ) 6 ] , L i 1 2 [ Z r 8 ( O 2 ) 1 2 ( O H ) 4 ( C 2 O 4 ) 8 ] , K 18 [Zr 12 (O 2 ) 18 (OH) 6 (C 2 O 4 ) 12 ], and Rb 24 [Zr 16 (O 2 ) 24 (OH) 8 (C 2 O 4 ) 16]. The Zr ring nuclearity increases with countercation size, while Hf polymerization decreases with increasing countercation size. The Zr rings feature nine-coordinate face-sharing polyhedra in both solution and the solid state, unprecedented in Zr coordination complexes. These studies describe differentiating the coordination chemistry of Zr/Hf, exploiting simple aqueous reagents that could be further developed for aqueous synthesis of materials as well as challenging chemical separations.

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ChemInform Abstract: Synthesis and Structure of Polynuclear Peroxofluorozirconates K6Zr3F12(O2)3·2 H2O2·2 H2O.

Abstract: The complex formation in the system ZrOCl2·8 H2O‐KF·2 H2O‐H2O2 is investigated by 19F NMR spectroscopy.

Cited by 2 publications

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Understanding the Scarcity of Thorium Peroxide Clusters

Understanding the Scarcity of Thorium Peroxide Clusters

Countercation-Controlled Nuclearity of Zr/Hf Peroxo Oxalates

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