Potassium, Cesium, and Ammonium Peroxogermanates with Inorganic Hexanuclear Peroxo Bridged Germanium Anion Isolated from Aqueous Solution

Medvedev, Alexander G.; Mikhaylov, Alexey A.; Churakov, Andrei V.; Vener, Mikhail V.; Tripol’skaya, T. A.; Cohen, Shmuel; Lev, Ovadia; Prikhodchenko, Petr V.

doi:10.1021/acs.inorgchem.5b01293

Cited by 33 publications

(47 citation statements)

References 80 publications

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“…It does not decompose during water release and remains in the structure even upon heating to 130–140 °C. A similar loss of solvated water molecules before cleavage of the bridging peroxo ligands also takes place for peroxoborate and was also recently reported for peroxogermanate …”

Section: Resultssupporting

confidence: 81%

“…We have noted in a recent article that this “law” holds true also for hydrogen peroxide coordination to boron, which is well documented, and for the coordination of tin(IV) and germanium(IV), which were studied by us. Peroxo coordinations take place only at high pH, resulting in the formation of hydroperoxo or peroxo complexes.…”

Section: Discussionmentioning

confidence: 72%

“…The bathochromic shift is typical for p‐block element peroxo complexes. It was observed in hexahydroperoxostannates, peroxoantimonate, and peroxogermanate (865, 868, and 872–874 cm −1 , respectively), and it is attributed to the effect of the coordinating heavy atom. The other Raman lines in Figure S3 are less relevant; they are attributed to Te−O vibrations (lines below 800 cm −1 ) and to NH and OH vibrations (above 1000 cm −1 ) in accordance with a previous study of tellurates …”

Section: Resultsmentioning

confidence: 96%

“…Peroxo coordinations take place only at high pH, resulting in the formation of hydroperoxo or peroxo complexes. The opposite is also true; detailed studies of gallium, boron, aluminum, and germanium at low pH hydrogen peroxide systems revealed no interaction between the corresponding p‐block elements and peroxide. In fact, the first molecular hydrogen peroxide coordination compound, [ n Bu 4 N][(Ts 3 tren)Zn(H 2 O 2 )] has only recently been structurally characterized by Scarborough, despite the large abundance of aqua complexes .…”

Section: Discussionmentioning

confidence: 99%

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Peroxide Coordination of Tellurium in Aqueous Solutions

Mikhaylov

Medvedev

Churakov

et al. 2016

Chemistry A European J

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Tellurium-peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH4 )4 Te2 (μ-OO)2 (μ-O)O4 (OH)2 (1) and (NH4 )5 Te2 (μ-OO)2 (μ-O)O5 (OH)⋅1.28 H2 O⋅0.72 H2 O2 (2) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single-crystal and powder X-ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te2 (μ-OO)2 (μ-O)O4 (OH)2 ](4-) . The structure of 2 consists of an unsymmetrical [Te2 (μ-OO)2 (μ-O)O5 (OH)](5-) anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te2 (μ-OO)2 (μ-O) fragment with one μ-oxo- and two μ-peroxo bridging groups. (125) Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3-40 %wt H2 O2 and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium-peroxide coordination in any aqueous system and the first report of inorganic tellurium-peroxo complexes. General features common to all reported p-block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates.

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Section: Resultssupporting

confidence: 81%

Section: Discussionmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 96%

Section: Discussionmentioning

confidence: 99%

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Peroxide Coordination of Tellurium in Aqueous Solutions

Mikhaylov

Medvedev

Churakov

et al. 2016

Chemistry A European J

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“…1-OH 2 ,which is very similar to acomplex reported by Borovik et al, [22] is an incommensurately modulated structure and is therefore represented as aball-and-stick model. [23][24][25][26][27] Thefirst-order decay of 1-H 2 O 2 contrasts the second-order decay mechanism of B,which bears the same ligand and counterion, and at the same starting concentration has ah alf-life of 10 4 s. [19] This comparison suggests that the redox-active nature of Mh as adramatic effect on the stability of M(H 2 O 2 )s pecies. For 1-OH 2 ,w hich only contains two second-sphere hydrogen bonds,t he Bu proton resonances overlap between 1and À1ppm.…”

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confidence: 99%

Hydrogen Peroxide Coordination to Cobalt(II) Facilitated by Second‐Sphere Hydrogen Bonding

et al. 2016

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M(H2 O2 ) adducts have been postulated as intermediates in biological and industrial processes; however, only one observable M(H2 O2 ) adduct has been reported, where M is redox-inactive zinc. Herein, direct solution-phase detection of an M(H2 O2 ) adduct with a redox-active metal, cobalt(II), is described. This Co(II) (H2 O2 ) compound is made observable by incorporating second-sphere hydrogen-bonding interactions between bound H2 O2 and the supporting ligand, a trianionic trisulfonamido ligand. Thermodynamics of H2 O2 binding and decay kinetics of the Co(II) (H2 O2 ) species are described, as well as the reaction of this Co(II) (H2 O2 ) species with Group 2 cations.

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Amphoteric Aqueous Hafnium Cluster Chemistry

et al. 2016

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Selective dissolution of hafnium-peroxo-sulfate films in aqueous tetramethylammonium hydroxidee nables extreme UV lithographic patterning of sub-10 nm HfO 2 structures.H afnium speciation under these basic conditions (pH > 10), however,i su nknown, as studies of hafnium aqueous chemistry have been limited to acid. Here,w er eport synthesis,crystal growth, and structural characterization of the first polynuclear hydroxo hafnium cluster isolated from base, [TMA] 6 [Hf 6 (m-O 2 ) 6 (m-OH) 6 (OH) 12 ]·38 H 2 O. The solution behavior of the cluster,i ncluding supramolecular assembly via hydrogen bonding is detailed via small-angle X-ray scattering (SAXS) and electrospray ionization mass spectrometry (ESI-MS). The study opens anew chapter in the aqueous chemistry of hafnium, exemplifying the concept of amphoteric clusters and informing ac ritical process in single-digit-nm lithography.Water-soluble molecular oxo-hydroxo metal clusters are recognized building blocks for deposition of functional thinfilm coatings,offering low energy and "green" processing. [1][2][3] Additionally,s elected hafnium-peroxo-sulfate clusters provide unprecedented dimensional control in nanolithography. [4,5] In this lithography,u nexposed oxo-hydroxo Hf regions dissolve in base,m eaning soluble hafnium species exist at high pH.Up to now,h owever,t he aqueous chemistry of hafnium has been documented only for strongly acidic conditions.I n mildly acidic conditions (pH ! 3), gels and precipitates result from rapid hydrolysis and condensation. [6,7] At low pH, oxohydroxo hafnium clusters are commonly stabilized and isolated with capping sulfate ligands,s ometimes linking clusters into 1, 2o r3 -dimensional networks.[ [12,13] Our interest in oxo-hydroxo hafnium speciation in base arises from the development step in lithographic patterning with the water-processed hafnium material known as HafSO x , formulated Hf 4 (OH) 6.4 (O 2 ) 2 (SO 4 ) 2.8 . [4,5,14] Nanolithography allows bulk semiconductors and metals to be shaped into computing devices with sub-10 nm features.[15] New inorganic resists,such as HafSO x ,offer ultra-high-resolution patterns. [6] There are two major steps in the patterning process with HafSOx:1)exposure,which causes dissociation of the peroxo ligand and induces condensation;and 2) development, where unexposed material is selectively dissolved in concentrated aqueous tetramethylammonium hydroxide (TMAH). The nature of the species produced in these basic solutions is unknown. This dissolution, coupled with stability of asimilar peroxo-phosphato-niobium cluster observed in both basic and acidic solutions [16] has led us to propose the concept of amphoteric clusters,w herein simple ligand sets stabilize as ingle cluster or similar clusters at the extreme ends of the pH scale.T his concept broadens the approach to cluster synthesis and study,asmost common cluster types exist across limited pH ranges.[17] Forexample,Group 13 polycations are currently known to exist in the narrow range pH 3-4; [18,19] V, Mo,and Wpolyoxom...

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Potassium, Cesium, and Ammonium Peroxogermanates with Inorganic Hexanuclear Peroxo Bridged Germanium Anion Isolated from Aqueous Solution

Cited by 33 publications

References 80 publications

Peroxide Coordination of Tellurium in Aqueous Solutions

Peroxide Coordination of Tellurium in Aqueous Solutions

Hydrogen Peroxide Coordination to Cobalt(II) Facilitated by Second‐Sphere Hydrogen Bonding

Amphoteric Aqueous Hafnium Cluster Chemistry

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