The structure of platinic acid

Scott, H. G.

doi:10.1107/s0567740879011171

Cited by 17 publications

(12 citation statements)

References 7 publications

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“…The calculated Pt–OH bond lengths of the [Pt(NO 3 ) n (OH) 6 − n ] 2‐ −( n = 1–6) complexes in aqueous solutions are found in the range of 1.992–2.131 Å. The calculated Pt–OH bond lengths of the platinic acid [Pt(OH) 6 ] 2− in aqueous solution found in the range of 2.055–2.064 Å are in excellent agreement with the experimental values of 2.06–2.11 Å determined by XRD studies on the H 2 [Pt(OH) 6 ] acid …”

Section: Resultssupporting

confidence: 79%

“…As far as the speciation of Pt(IV) complexes in aqueous nitric acid solutions is concerned there are little data available. The dissolution of platinic acid H 2 [Pt(OH) 6 ] in concentrated HNO 3 leads to so called ‘platinum nitrate’ (CAS No. 18496‐40‐7) of uncertain nature, widely used for the preparation of heterogeneous catalysts .…”

Section: Introductionmentioning

confidence: 99%

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Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Tsipis

Karapetsas

2016

Magnetic Reson in Chemistry

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(195) Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO3 )n (OH)6 - n ](2-) , [Pt(NO3 )n (OH2 )6 - n ](4 - n) (n = 1-6), and [Pt(NO3 )6 - n - m (OH)m (OH2 )n ](-2 + n - m) formed by dissolution of platinic acid, H2 [Pt(OH)6 ], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge-including atomic orbitals (GIAO)-PBE0/segmented all-electron relativistically contracted-zeroth-order regular approximation (SARC-ZORA)(Pt) ∪ 6-31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second-order polynomial plots of δcalcd ((195) Pt) versus δexptl ((195) Pt) chemical shifts and δcalcd ((195) Pt) versus the natural atomic charge QPt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ (195) Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σ(iso) (195) Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ (195) Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter-ion effects on the (195) Pt NMR chemical shifts of the anionic [Pt(NO3 )n (OH)6 - n ](2-) and cationic [Pt(NO3 )n (OH2 )6 - n ](4 - n) (n = 0-3) complexes we calculated the (195) Pt NMR chemical shifts of the neutral (PyH)2 [Pt(NO3 )n (OH)6 - n ] (n = 1-6; PyH = pyridinium cation, C5 H5 NH(+) ) and [Pt(NO3 )n (H2 O)6 - n ](NO3 )4 - n (n = 0-3) complexes. Counter-anion effects are very important for the accurate prediction of the (195) Pt NMR chemical shifts of the cationic [Pt(NO3 )n (OH2 )6 - n ](4 - n) complexes, while counter-cation effects are less important for the anionic [Pt(NO3 )n (OH)6 - n ](2-) complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Tsipis

Karapetsas

2016

Magnetic Reson in Chemistry

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“…It has also been demonstrated clearly that the hydrous Pt oxide layer grown in alkaline solutions does not differ significantly in structure and composition from the acid-grown deposit [18,19] . The composition of the thick oxide layer has been described as essentially the anion of platinic acid, H 2 Pt(OH)6 [19], since this acid and its salts have been characterized in the bulk state by X-ray techniques [28]. In the case of thick oxide layers formed in alkaline solutions, the first layer is electroreduced voltammetrically at 0 .6 V [18,19], whereas the thicker layer, which appears under low f and high E" limits as a yellow film, is not reduced above 0 V (RHE) during the negative sweep, although part of the material existing beneath the yellow hydrous film is presumably electroreduced at 0 .25 V [19].…”

Section: Discussionmentioning

confidence: 99%

Changes in the surface morphology of platinum electrodes produced by the application of periodic potential treatments in alkaline solution

Visintín

Triaca

Arvía

1990

Journal of Electroanalytical Chemistry and Interfacial Electroc

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The development of preferentially oriented crystalline surfaces of Pt with rough topographies in alkaline solution, produced by the application of periodic square wave potential treatments, is described . The influence of the different electrical variables is studied systematically and the characteristics of the different growth modes are followed through voltammetry in the H-atom electrosorption potential range and SEM micrographs . These effects are explained in terms of a strong OH -ion-metal surface interaction which favours the formation of hydrous Pt oxide layers . The electroreduction of the latter yields Pt overlayers with distinguishable growth modes and preferred crystalline orientations .

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“…These two compounds differ only in the protonation state of the PtW 6 species. 2A 16 To confirm this hypothesis, we measured the 195 Pt MAS spectra of the potassium salt K 2 [Pt IV (OH) 6 ], which contains a more symmetrical [Pt IV (OH) 6 ] 2À unit. 4 Firstly, we performed the 195 Pt MAS NMR measurements on the Pt IV precursor complex H 2 [Pt IV (OH) 6 ], in order to determine optimal parameters for the follow-up measurements.…”

Section: Introductionmentioning

confidence: 99%

Characterization of Pt^IV-containing polyoxometalates by high-resolution solid-state¹⁹⁵Pt and⁵¹V NMR spectroscopy

et al. 2016

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We report on the feasibility of applying high-resolution solid-state 195 Pt MAS NMR spectroscopy for several Pt IV -containing polyoxotungstates, and of 195 Pt as well as 51 V for a Pt IV -containing polyoxovanadate. This method is particularly useful for polyanions which are unstable in solution and/or poorly soluble, as well as for systems exhibiting crystallographic disorder of Pt and W sites. We also report solution 195 Pt and 183 W NMR spectra of hexatungstoplatinate(IV) [H 3 PtW 6 O 24 ] 5À for the first time.

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The structure of platinic acid

Cited by 17 publications

References 7 publications

Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Changes in the surface morphology of platinum electrodes produced by the application of periodic potential treatments in alkaline solution

Characterization of Pt^IV-containing polyoxometalates by high-resolution solid-state¹⁹⁵Pt and⁵¹V NMR spectroscopy

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The structure of platinic acid

Cited by 17 publications

References 7 publications

Prediction of195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Prediction of195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Changes in the surface morphology of platinum electrodes produced by the application of periodic potential treatments in alkaline solution

Characterization of PtIV-containing polyoxometalates by high-resolution solid-state195Pt and51V NMR spectroscopy

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Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Prediction of¹⁹⁵Pt NMR chemical shifts of dissolution products of H₂[Pt(OH)₆] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

Characterization of Pt^IV-containing polyoxometalates by high-resolution solid-state¹⁹⁵Pt and⁵¹V NMR spectroscopy