Stability of xenon(II) compounds. Pentafluorooxyselenium and pentafluorooxytellurium radicals. Bis(pentafluorotellurium) peroxide and chlorine pentafluoroorthotellurate

Seppelt, Konrad; Nöthe, D.

doi:10.1021/ic50129a046

Cited by 69 publications

(28 citation statements)

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“…[31] Comparison with noble-gas teflate complexes provides further support for our optimistic view on the possible preparation of Hg IV teflate systems: Xe(OTeF 5 ) 2 exhibits surprisingly high thermal stability and decomposes only above about 130 8C (Xe(OSeF 5 ) 2 is only slightly less stable). [31,40] Nevertheless, our computations show that Xe(OTeF 5 ) 2 is endothermic with respect to elimination of (OTeF 5 ) 2 , with a reaction energy in a similar range as computed for the Hg IV complexes (Table 8). Similarly, Xe(OTeF 5 ) 4 is well known but computed to eliminate (OTeF 5 ) 2 with even slightly higher exothermicity than Hg(OTeF 5 ) 4 (cf.…”

Section: Discussion and Suggestions For Experimental Investigationsupporting

confidence: 65%

“…One might expect, [31] that this is due to the relatively strong O À O bonds in the peroxides F 5 EOOEF 5 compared to the weaker FÀF bond in F 2 . [39,40] However, the peroxide OÀO bonds are only about 15-20 kJ mol À1 more stable than the FÀF bond ( Table 5). This is clearly not enough to explain the much more facile elimination of X 2 compared to F 2 .…”

Section: Thermochemical Stability Of Hg IV Versus Hg Ii Complexesmentioning

confidence: 99%

“…[31,40] They might be a good starting point. A variety of suitable reagents for oxidations are available, including Xe(OTeF 5 ) 2 , [31,40] Xe(OTeF 5 ) 4 , [34] or the recently reported [XeOTeF 5 ][Sb(OTeF 5 ) 6 ]. [43] B(OTeF 5 ) 3 is also a well-known reagent for transferring the OTeF 5 ligand.…”

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confidence: 99%

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Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Riedel

Straka

Kaupp

2005

Chemistry A European J

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While the thermochemical stability of gas-phase HgF4 against F2 elimination was predicted by accurate quantum chemical calculations more than a decade ago, experimental verification of "truly transition-metal" mercury(IV) chemistry is still lacking. This work uses detailed density functional calculations to explore alternative species that might provide access to condensed-phase Hg(IV) chemistry. The structures and thermochemical stabilities of complexes Hg(IV)X4 and Hg(IV)F2X2 (X- = AlF4-, Al2F7-, AsF6-, SbF6-, As2F11-, Sb2F11-, OSeF5-, OTeF5-) have been assessed and are compared with each other, with smaller gas-phase HgX4 complexes, and with known related noble gas compounds. Most species eliminate F2 exothermically, with energies ranging from only about -60 kJ mol(-1) to appreciable -180 kJ mol(-1). The lower stability of these species compared to gas-phase HgF4 is due to relatively high coordination numbers of six in the resulting Hg(II) complexes that stabilize the elimination products. Complexes with AsF6 ligands appear more promising than their SbF6 analogues, due to differential aggregation effects in the Hg(II) and Hg(IV) states. HgF2X2 complexes with X- = OSeF5- or OTeF5- exhibit endothermic fluorine elimination and relatively weak interactions in the Hg(II) products. However, elimination of the peroxidic (OEF5)2 coupling products of these ligands provides an alternative exothermic elimination pathway with energies between -120 and -130 kJ mol(-1). While all of the complexes investigated here thus have one exothermic decomposition channel, there is indirect evidence that the reactions should exhibit nonnegligible activation barriers. A number of possible synthetic pathways towards the most interesting condensed-phase Hg(IV) target complexes are proposed.

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Section: Discussion and Suggestions For Experimental Investigationsupporting

confidence: 65%

Section: Thermochemical Stability Of Hg IV Versus Hg Ii Complexesmentioning

confidence: 99%

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Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Riedel

Straka

Kaupp

2005

Chemistry A European J

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“…Glassware was greased with Triboflon III. The pentafluoroorthotelluric acid HOTeF 5 , [43] triethylgallium GaEt 3 , [44] and AgOTeF 5 [45] were prepared as described elsewhere. Gallium trichloride was synthesized as follows:ACl 2 bottle and aS chlenk flask loaded with 4gmolten Ga metal were connected to aS chlenk line and the entire connection and the Schlenk flask were evacuated and kept under static vacuum.…”

Section: Methodsmentioning

confidence: 99%

Oxygen‐Bridged Ga₂(Et)₃(OTeF₅)₃ and the Weakly Coordinating Anions [Ga(Et)(OTeF₅)₃]⁻ and [Ga(OTeF₅)₄]⁻

Wiesner

Fischer

Steinhauer

et al. 2019

Chemistry A European J

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Salts of the weakly coordinating anions [Ga(OTeF 5 ) 4 ] À as well as [Ga(Et)(OTeF 5 ) 3 ] À and the neutral Ga 2 (Et) 3 (OTeF 5 ) 3 were synthesized and characterized by spectroscopic methodsa nd single-crystal X-ray diffraction. Ga 2 (Et) 3 (OTeF 5 ) 3 was formed by treating GaEt 3 with pentafluoroorthotelluric acid (HOTeF 5 )a nd reacted with PPh 4 Cl and CPh 3 Cl to [PPh 4 ][Ga(Et)(OTeF 5 ) 3 ]a nd [CPh 3 ][Ga(Et)(OTeF 5 ) 3 ]. In contrast, Ag[Ga(OTeF 5 ) 4 ]w as prepared from AgOTeF 5 and GaCl 3 and was used as av ersatile startingm aterial for furtherr eactions. Starting with Ag[Ga(

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“…: Xe 8,4 (gef. : 9,7); Te 49,O (49,O); F 36,5 (36,4) [32] . Es gab keinen Hinweis auf ein xenonhaltiges Radikal.…”

Section: Darstellung Von X C ( O T C F~unclassified

Edelgasverbindungen mit dem Liganden –OTeF₅

Jacob¹,

Lentz²,

Seppelt

et al. 1981

Zeitschrift anorg allge chemie

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Die Verbindungen Xe(OTeF5)4, Xe(OTeF5)6, OXe(OTeF5)4 sowie gemischt substituierte Derivate OXeFx(OTeF5)4−x werden beschrieben und im Zusammenhang mit den älteren Verbindungen Xe(OTeF5)2 und Xe(OSeF5)2 diskutiert. Der Ligand —OTeF5 wird nur von Fluor übertroffen in seinem Vermögen, Edelgasverbindungen zu stabilisieren. Während die Strukturen von Xe(OTeF5)4 und OXe(OTeF5)4 als XeF4 und XeOF4 Analoga keine Probleme aufwerfen, erweist sich Xe(OTeF5)6 als Analogon zum monomeren (gasförmigen) XeF6. Versuche zur Darstellung von Kryptonverbindungen waren nicht erfolgreich.

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Stability of xenon(II) compounds. Pentafluorooxyselenium and pentafluorooxytellurium radicals. Bis(pentafluorotellurium) peroxide and chlorine pentafluoroorthotellurate

Abstract: Die Verbindungen Xe(OXF5 )2(X: Se, Te) sind die thermisch stabilsten der bisher bekannten Xe(OR)2‐ Verbindungen.

Cited by 69 publications

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Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Oxygen‐Bridged Ga₂(Et)₃(OTeF₅)₃ and the Weakly Coordinating Anions [Ga(Et)(OTeF₅)₃]⁻ and [Ga(OTeF₅)₄]⁻

Edelgasverbindungen mit dem Liganden –OTeF₅

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Stability of xenon(II) compounds. Pentafluorooxyselenium and pentafluorooxytellurium radicals. Bis(pentafluorotellurium) peroxide and chlorine pentafluoroorthotellurate

Abstract: Die Verbindungen Xe(OXF5 )2(X: Se, Te) sind die thermisch stabilsten der bisher bekannten Xe(OR)2‐ Verbindungen.

Cited by 69 publications

References 0 publications

Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Oxygen‐Bridged Ga2(Et)3(OTeF5)3 and the Weakly Coordinating Anions [Ga(Et)(OTeF5)3]− and [Ga(OTeF5)4]−

Edelgasverbindungen mit dem Liganden –OTeF5

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Oxygen‐Bridged Ga₂(Et)₃(OTeF₅)₃ and the Weakly Coordinating Anions [Ga(Et)(OTeF₅)₃]⁻ and [Ga(OTeF₅)₄]⁻

Edelgasverbindungen mit dem Liganden –OTeF₅