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Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of α- and β-O2Sn2F9, O2Sn2F9·0.9HF, O2GeF5·HF, and O2[Hg(HF)]4(SbF6)9.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-16 , DOI: 10.1021/acs.inorgchem.9b03518 Zoran Mazej 1 , Evgeny Goreshnik 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-16 , DOI: 10.1021/acs.inorgchem.9b03518 Zoran Mazej 1 , Evgeny Goreshnik 1
Affiliation
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By treating gaseous, liquid, or solid fluorides with UV-photolyzed O2/F2 mixtures and by treating solid oxides with UV-photolyzed F2 (or O2/F2 mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O2MIIIF4 (M = B, Fe, Co, Ag), O2MIVF5 (M = Ti, Sn, Pb), (O2)2MIVF6 (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O2MIV2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV2F11 (M = Pt), O2MVIF7 (M = Se), (O2)2MVIF8 (M = Mo, W), and O2MVIIF8 (M = I). The approach has been successful in the case of previously known O2BF4, O2MF6 (M = As, Sb, Au; Pt), O2GeF5, and (O2)2(Ti7F30). Novel compounds O2GeF5·HF, α-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of β-O2Sn2F9 (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF6 (M = Ge, Sn) units. The anion in the crystal structure of O2GeF5·HF is comprised of infinite ([GeF5]-)∞ chains of GeF6 octahedra that share common vertices. The HF molecules and O2+ cations are located between the chains. The crystal structure of α-O2SnF9 (1-D) is constructed from [O2]+ cations and polymeric ([Sn2F9]-)∞ anions which appear as two parallel infinite chains comprised of SnF6 units, where each SnF6 unit of one chain is connected to a SnF6 unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O2][Sn2F9]·0.9HF reveals that it is comprised of two-dimensional ([Sn2F9]-)∞ grids with [O2]+ cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn2F9]-)∞ layer contains both six- and seven-coordinated Sn(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O2]+ salt, O2[Hg(HF)]4[SbF6]9, was prepared. In its crystal structure, the Hg atoms bridge to SbF6 units to form a 3-D framework. The O2+ cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O2+ fluorine salts (i.e., O2TiCl5 and O2MCl6 (M = Nb, Sb)) failed.
中文翻译：
在液态无水氟化氢中通过光化学反应合成双氧盐：α-和β-O2Sn2F9，O2Sn2F9·0.9HF，O2GeF5·HF和O2 [Hg（HF）] 4（SbF6）9的X射线晶体结构。
通过用UV光解的O2 / F2混合物处理气态，液体或固体氟化物，并通过在环境温度下于液态无水HF中用UV光解的F2（或O2 / F2混合物）处理固体氧化物，我们研究了制备O2MIIIF4（M = B，Fe，Co，Ag），O2MIVF5（M = Ti，Sn，Pb），（O2）2MIVF6（M = Ti，Ge，Sn，Pb，Pd，Ni，Mn），O2MIV2F9（M = Sn），O2MVF6（M = As，Sb，Au，Pt），O2MV2F11（M = Pt），O2MVIF7（M = Se），（O2）2MVIF8（M = Mo，W）和O2MVIIF8（M = I）。在先前已知的O2BF4，O2MF6（M = As，Sb，Au; Pt），O2GeF5和（O2）2（Ti7F30）的情况下，该方法已经成功。合成了新型化合物O2GeF5·HF，α-O2Sn2F9（1-D）和HF溶剂化和非溶剂化形式的β-O2Sn2F9（2-D），并使用单晶X射线衍射确定了其晶体结构。所有这些材料的晶体结构都来自八面体MF6（M = Ge，Sn）单元的缩合。O2GeF5·HF晶体结构中的阴离子由共享共同顶点的GeF6八面体的无限（[GeF5]-）∞链组成。HF分子和O2 +阳离子位于链之间。α-O2SnF9（1-D）的晶体结构由[O2] +阳离子和聚合的[[Sn2F9]-）∞阴离子构成，它们显示为由SnF6单元组成的两条平行无穷链，其中一条链的每个SnF6单元为通过共享的氟顶点连接到第二链的SnF6单元。[O2] [Sn2F9]·0.9HF的单晶结构测定表明，它由带有[O2] +阳离子和HF分子的二维（[Sn2F9]-）∞网格组成。二维栅格具有波状构型。（[Sn2F9]-）∞层包含六个和七个配位的Sn（IV）原子，这些原子通过桥接氟原子相互连接。制备了新的，更复杂的[O2] +盐O2 [Hg（HF）] 4 [SbF6] 9。在其晶体结构中，Hg原子桥接至SbF6单元以形成3-D骨架。O2 +阳离子位于空隙内部，而HF分子通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。O2 +阳离子位于空隙内部，而HF分子通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。O2 +阳离子位于空隙内部，而HF分子则通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。
更新日期：2020-01-16
中文翻译：
在液态无水氟化氢中通过光化学反应合成双氧盐：α-和β-O2Sn2F9，O2Sn2F9·0.9HF，O2GeF5·HF和O2 [Hg（HF）] 4（SbF6）9的X射线晶体结构。
通过用UV光解的O2 / F2混合物处理气态，液体或固体氟化物，并通过在环境温度下于液态无水HF中用UV光解的F2（或O2 / F2混合物）处理固体氧化物，我们研究了制备O2MIIIF4（M = B，Fe，Co，Ag），O2MIVF5（M = Ti，Sn，Pb），（O2）2MIVF6（M = Ti，Ge，Sn，Pb，Pd，Ni，Mn），O2MIV2F9（M = Sn），O2MVF6（M = As，Sb，Au，Pt），O2MV2F11（M = Pt），O2MVIF7（M = Se），（O2）2MVIF8（M = Mo，W）和O2MVIIF8（M = I）。在先前已知的O2BF4，O2MF6（M = As，Sb，Au; Pt），O2GeF5和（O2）2（Ti7F30）的情况下，该方法已经成功。合成了新型化合物O2GeF5·HF，α-O2Sn2F9（1-D）和HF溶剂化和非溶剂化形式的β-O2Sn2F9（2-D），并使用单晶X射线衍射确定了其晶体结构。所有这些材料的晶体结构都来自八面体MF6（M = Ge，Sn）单元的缩合。O2GeF5·HF晶体结构中的阴离子由共享共同顶点的GeF6八面体的无限（[GeF5]-）∞链组成。HF分子和O2 +阳离子位于链之间。α-O2SnF9（1-D）的晶体结构由[O2] +阳离子和聚合的[[Sn2F9]-）∞阴离子构成，它们显示为由SnF6单元组成的两条平行无穷链，其中一条链的每个SnF6单元为通过共享的氟顶点连接到第二链的SnF6单元。[O2] [Sn2F9]·0.9HF的单晶结构测定表明，它由带有[O2] +阳离子和HF分子的二维（[Sn2F9]-）∞网格组成。二维栅格具有波状构型。（[Sn2F9]-）∞层包含六个和七个配位的Sn（IV）原子，这些原子通过桥接氟原子相互连接。制备了新的，更复杂的[O2] +盐O2 [Hg（HF）] 4 [SbF6] 9。在其晶体结构中，Hg原子桥接至SbF6单元以形成3-D骨架。O2 +阳离子位于空隙内部，而HF分子通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。O2 +阳离子位于空隙内部，而HF分子通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。O2 +阳离子位于空隙内部，而HF分子则通过F原子与Hg原子结合。尝试制备几种O2 +氟盐的氯类似物（即O2TiCl5和O2MCl6（M = Nb，Sb））失败。
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