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首页> 外文期刊>Journal of Fluorine Chemistry >The room temperature preparation of metastable fluorides and potent oxidizers
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The room temperature preparation of metastable fluorides and potent oxidizers

机译：亚稳态氟化物和强氧化剂的室温制备

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The low electronegativity of an oxidation state in an anion enables high oxidation states,e.g.Ni~(IV),and Ag~(III),to be easily attained in liquid anhydrous HF (aHF),made basic with fluoride-ion donors.The oxidation state can be enhanced if elemental fluorine is photo-dissociated.Teflon~R valves and lines,especially transparent and kinetically stable fluorocarbon containers for the aHF solutions,provide for this.Binary fluorides that are of low solubility in aHF,can be displaced by stronger F~- acceptors from their high oxidation-state anions.NiF_4,NiF_3,and AgF_3,which can be made in this manner,are thermodynamically unstable with respect to loss of fluorine.The electronegativity of the oxidation state in the binary fluoride is higher than in the anion (hence the metastability) and when a strong F~- acceptor converts the binary fluoride into a cationic species,the electronegativity is further enhanced.Thus cationic Ag~(III) and Ni~(IV) are superior to KrF~+,as one-electron oxidizers and are the most potent oxidizers known thus far.They are able to remove the electron from all platinum-metal hexafluoro-anions,MF_6~-,to liberate the hexafluorides.All of this chemistry can be achieved at or below room temperature.
机译：阴离子中氧化态的低电负性可在由氟化物离子供体制成的液态无水HF（aHF）中轻松获得高氧化态，例如Ni〜（IV）和Ag〜（III）。如果将元素氟进行光离解，则可以提高氧化态。为此，提供了特氟隆R阀和管线，特别是用于aHF溶液的透明且具有动力学稳定性的碳氟化合物容器。在aHF中溶解度低的二元氟化物可以被取代可以通过这种方式制得的NiF_4，NiF_3和AgF_3的高氧化态阴离子使其具有更强的F〜-受体，它们对于氟的流失是热力学不稳定的。二元氟化物中氧化态的电负性更高比阴离子（因此具有亚稳性）和强F〜-受体将二元氟化物转化为阳离子物种时，电负性进一步增强。因此，阳离子Ag〜（III）和Ni〜（IV）优于KrF〜 +，作为单电子氧化剂a这是迄今为止已知的最有效的氧化剂。它们能够从所有铂金属六氟阴离子MF_6〜-中除去电子，以释放六氟化物。所有这些化学反应均可在室温或低于室温的条件下实现。

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