Facile Routes to NiF62-, AgF4-, AuF6-, and PtF6- Salts Using O2+ as a Source of O2F in Anhydrous HF

Facile Routes to NiF62-, AgF4-, AuF6-, and PtF6- Salts Using O2+ as a Source of O2F in Anhydrous HF
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使用 O2 作为无水 HF 中的 O2F 来源,轻松制备 NiF62-、AgF4-、AuF6- 和 PtF6- 盐

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发表时间:
1998
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通讯作者:
N. Bartlett
N. Bartlett
中科院分区:
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作者:
G. Lucier;C. Shen;S. H. Elder;N. Bartlett

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在20 °C或更低温度下,溶解在液体无水氟化氢(aHF)中的O2+盐将PtF 62-的aHF溶液氧化为PtF 6-。在aHF(O2 F(solv))中,由碱金属氟化物生成的O2+盐的母体碱在−50 °C以下是长寿命的。在低于−50 °C时,O2 F的aHF溶液(solv)将Au(III)氧化为Au(V)(2 O2 F(solv)+AuF 4-(solv)→ AuF 6-(solv)+2O2(g))。在用碱金属氟化物制成碱性的aHF中,用悬浮的AgF 2或NiF 2原位生成O2 F(solv)(O2+(solv)+ F-(solv)→ O2 F(solv)),得到AgF 4-和NiF 62-盐。AAsF 6(A = Cs,K)在aHF中的低溶解度提供了在aHF中的(O2)2 PdF 6溶液的复分解制备。即使在-60 °C下,去除aHF也会导致一些O2和F2损失,形成接近(O2)PdF 5的组成。
O2+ salts dissolved in liquid anhydrous hydrogen fluoride (aHF) at 20 °C or below oxidize aHF solutions of PtF62- to PtF6-. The parent base of O2+ salts in aHF (O2F(solv)) generated with alkali fluoride is long-lived below −50 °C. An aHF solution of O2F(solv) oxidizes Au(III) to Au(V) below −50 °C (2O2F(solv) + AuF4-(solv) → AuF6-(solv) +2O2(g)). In situ generation of O2F(solv) (O2+(solv) + F-(solv) → O2F(solv)) with AgF2 or NiF2 in suspension in the aHF made basic with alkali fluoride gives AgF4- and NiF62-salts. Low solubility of AAsF6(A = Cs, K) in aHF provides for the metathetical preparation of (O2)2PdF6 solutions in aHF. Removal of aHF, even at −60 °C, results in some O2 and F2 loss, to a composition approaching (O2)PdF5.