Selenium(IV) fluoride and oxofluoride anions

Dixon, David A.; Haiges, Ralf; Hopfinger, Mathias; Jackson, Virgil E.; Klapötke, Thomas M.; Krumm, Burkhard; Scherr, Matthias

doi:10.1016/j.jfluchem.2010.04.009

Cited by 7 publications

(10 citation statements)

References 92 publications

(94 reference statements)

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“…The SeF bond length in Trip 2 C 6 H 3 SeF is fairly short, 168.23(5) pm and resembles the bond length to the equatorial F atom in SeF 4 ,24 168.2 pm (gas phase) and in the SeOF 3 − ion,25 176.68 pm. Mes 2 SeF 2 26 with 188.87 and 187.76 pm and bis(2,2‐biphenylen)selenium difluoride27 with 185.3 pm have longer SeF bonds.…”

Section: Se 125te and 19f Nmr Data [Ppm Hz] Of The Se‐f And Te‐fmentioning

confidence: 83%

Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride

et al. 2011

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Joining the stable: The first examples of the highly instable selenenyl fluorides RSeF are prepared from the reaction on the tin selenide RSeSnMe(3) with XeF(2). Through the use of extremely large protecting groups (m-terphenyl ligands) which stabilizes the RSeF units against disproportionation, the compounds could be isolated and characterized by NMR spectroscopy and single-crystal structure analysis (see structure).

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Section: Se 125te and 19f Nmr Data [Ppm Hz] Of The Se‐f And Te‐fmentioning

confidence: 83%

Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride

et al. 2011

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“…There is significant interest in the thermochemical properties including bond dissociation energies (BDEs) of compounds of the main group elements of the second- and higher-rows. , There have been a number of structural and spectroscopic studies of the binary selenium fluorides SeF 4 , − SeF 5 – , ,, and SeF 6 2– , , and the selenium oxofluorides including SeOF 2 , ,− SeO 2 F – , ,− and SeOF 3 – . ,− Octahedral SeF 6 has been studied extensively, and its geometry, heat of formation, vibrational frequencies, and 77 Se NMR chemical shifts − have been reported. The crystal structure of a compound of the form RSeF with R a phenyl ring with large bulky substituents was just reported .…”

Section: Introductionmentioning

confidence: 99%

“…Calculated frequencies for other molecules can be found in our previous report. 2 NMR Chemical Shifts. The chemical shifts are given in Table 4 with different exchange-correlation functionals and basis sets: B3LYP/AhlrichsVTZP, BLYP/TZ2P, and at the ZORA-BLYP/TZ2P level.…”

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confidence: 99%

Thermochemical Properties of Selenium Fluorides, Oxides, and Oxofluorides

Jackson

Dixon

2012

Inorg. Chem.

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The bond dissociation energies (BDEs), fluoride and fluorocation affinities, and electron affinities of SeF(n) (n = 1-6), SeOF(n) (n = 0-4), and SeO(2)F(n) (n = 0-2) have been predicted with coupled cluster CCSD(T) theory extrapolated to the complete basis set limit. To achieve near chemical accuracy, additional corrections were added to the complete basis set binding energies based on frozen core coupled cluster theory energies. These included corrections for core-valence effects, scalar relativistic effects, for first-order atomic spin-orbit effects, and vibrational zero point energies. The adiabatic BDEs contain contributions from product reorganization energies and, therefore, can be much smaller than the diabatic BDEs and can vary over a wide range. For thermochemical calculations, the adiabatic values must be used, whereas for bond strength and kinetic considerations, the diabatic values should be used when only small displacements of the atoms without change of the geometry of the molecule are involved. The adiabatic Se-F BDEs of SeF(n) (n = 1-6) are SeF(6) = 90, SeF(5) = 27, SeF(4) = 93, SeF(3) = 61, SeF(2) = 86, and SeF = 76 kcal/mol, and the corresponding diabatic values are SeF(6) = 90, SeF(5) = 88, SeF(4) = 93, SeF(3) = 74, SeF(2) = 86, and SeF = 76 kcal/mol. The adiabatic Se-O BDEs of SeO(n) (n = 1-3), SeOF(n) (n = 1-4), and SeO(2)F(n) (n = 1,2) range from 23 to 107 kcal/mol, whereas the diabatic ones range from 62 to 154 kcal/mol. The adiabatic Se-F BDEs of SeOF(n) (n = 1-4) and SeO(2)F(n) (n = 1,2) range from 20 to 88 kcal/mol, whereas the diabatic ones range from 73 to 112 kcal/mol. The fluoride affinities of SeF(n), (n = 1-6), SeO(n), (n = 1-3), SeOF(n), (n = 1-4), and SeO(2)F(n) (n = 1,2) range from 15 to 121 kcal/mol, demonstrating that the Lewis acidity of these species covers the spectrum from very weak (SeF(6)) to very strong (SeO(3)) acids. The electron affinities which are a measure of the oxidizing power of a species, span a wide range from 1.56 eV in SeF(4) to 5.16 eV in SeF(5) and for the free radicals are much higher than for the neutral molecules. Another interesting feature of these molecules and ions stems from the fact that many of them possess both a Se free valence electron pair and a free unpaired valence electron, raising the questions of their preferred location and their influence on the Se-F and Se═O bond strengths.

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“…Using this modified method tetraphenylarsonium perruthenate ( 14 ) and bis(triphenylphosphoranylidene) ammonium perruthenate ( 15 ) (isomorphous with the SeF 3 O − analogue) were synthesised in 29 and 93 % yield, respectively (Table , see Supporting Information for X‐ray crystallographic analysis). However, room temperature stability was only observed for approximately 7 days.…”

Section: Methodsmentioning

confidence: 99%

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

Moore

Read

Bernhardt

et al. 2018

Chemistry A European J

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The Ley-Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.

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Selenium(IV) fluoride and oxofluoride anions

Cited by 7 publications

References 92 publications

Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride

Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride

Thermochemical Properties of Selenium Fluorides, Oxides, and Oxofluorides

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

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Selenium(IV) fluoride and oxofluoride anions

Cited by 7 publications

References 92 publications

Trip2C6H3SeF: The First Isolated Selenenyl Fluoride

Trip2C6H3SeF: The First Isolated Selenenyl Fluoride

Thermochemical Properties of Selenium Fluorides, Oxides, and Oxofluorides

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

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Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride

Trip₂C₆H₃SeF: The First Isolated Selenenyl Fluoride