当前位置：
X-MOL 学术
›
Eur. J. Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Guanidinium Perfluoridotitanate(IV) Compounds: Structural Determination of an Oligomeric [Ti6F27]3– Anion, and an Example of a Mixed‐Anion Salt Containing Two Different Fluoridotitanate(IV) Anions
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2018-12-17 , DOI: 10.1002/ejic.201801207 Igor M. Shlyapnikov 1, 2 , Evgeny A. Goreshnik 1 , Zoran Mazej 1
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2018-12-17 , DOI: 10.1002/ejic.201801207 Igor M. Shlyapnikov 1, 2 , Evgeny A. Goreshnik 1 , Zoran Mazej 1
Affiliation
|
Chemical reactions between guanidinium carbonate or guanidinium chloride and titanium tetrafluoride in anhydrous hydrogen fluoride (aHF) were studied. The obtained products were recrystallized from saturated HF, SO2 and CH3CN solutions. Single‐crystal growths resulted in the detection of seven perfluoridotitanate(IV) compounds, which were structurally characterized. Three of them correspond to the phases obtained as the main products of the synthesis in aHF, i.e., [C(NH2)3]2[TiF6], [C(NH2)3]4[Ti4F20], and [C(NH2)3][Ti2F9]. When the guanidinium salt/TiF4 molar ratios were greater than 1:2, the resulting products were only sparingly soluble or completely insoluble in aHF. Therefore, single‐crystal growths were attempted from other aprotic solvents (SO2 and CH3CN). Single crystals of [C(NH2)3]3[Ti6F27]·SO2 were detected in the case of the former and [C(NH2)3]4[H3O]4[Ti4F20][TiF5]4 in the case of the latter. The presence of [H3O]+ can be explained by a contamination with traces of H2O, which is protonated in the superacid aHF. The same reason applies to the formation of the by‐products [H5O2]4[Ti8F36] and β‐[H3O][Ti2F9]. The crystal structures of the new guanidinium‐perfluoridotitanate(IV) compounds consist of oligomeric [Ti4F20]4–, [Ti6F27]3– and [Ti8F36]4–, as well as polymeric ([TiF5]–)∞ and ([Ti2F9]–)∞ perfluoridotitanate(IV) anions. The hexameric [Ti6F27]3– anion with a trigonal prismatic geometry was structurally determined for the first time. The crystal‐structure determination of the [C(NH2)3]4[H3O]4[Ti4F20][TiF5]4 revealed the first example of a mixed‐anion perfluoridotitanate(IV) compound containing two different perfluoridotitanate(IV) anions, i.e., oligomeric [Ti4F20]4– and 1‐D polymeric ([TiF5]–)∞ anions. The crystal structure of the guanidinium hydrogen difluoride salt [C(NH2)3][HF2] is also reported.
中文翻译：
胍基全氟钛酸（IV）化合物：低聚[Ti6F27] 3-阴离子的结构测定，以及包含两种不同氟钛酸（IV）阴离子的混合阴离子盐的实例
研究了碳酸胍或氯化胍与四氟化钛在无水氟化氢（aHF）中的化学反应。将获得的产物从饱和的HF，SO 2和CH 3 CN溶液中重结晶。单晶生长导致检测到七种全氟钛酸盐（IV）化合物，这些化合物具有结构特征。其中三个对应于在aHF中作为合成主要产物而获得的相，即[C（NH 2）3 ] 2 [TiF 6 ]，[C（NH 2）3 ] 4 [Ti 4 F 20 ]，和[C（NH 2）3] [Ti 2 F 9 ]。当胍盐/ TiF 4摩尔比大于1：2时，所得产物仅微溶于aHF或完全不溶于aHF。因此，尝试使用其他非质子传递溶剂（SO 2和CH 3 CN）进行单晶生长。在前者和[C（NH 2）3 ] 4 [H 3 O] 4 [Ti 4 F 20 ]的情况下，检测到[C（NH 2）3 ] 3 [Ti 6 F 27 ] · SO 2单晶。在后者的情况下为[TiF 5 ] 4。[H 3 O] +的存在可以用在超酸aHF中质子化的痕量H 2 O污染来解释。形成副产物[H 5 O 2 ] 4 [Ti 8 F 36 ]和β-[H 3 O] [Ti 2 F 9 ]的原因相同。新的胍基全氟钛酸酯（IV）化合物的晶体结构由低聚的[Ti 4 F 20 ] 4–，[Ti 6 F 27 ]组成3–和[Ti 8 F 36 ] 4–以及聚合（[TiF 5 ] –）∞和（[Ti 2 F 9 ] –）∞全氟钛酸（IV）阴离子。首次在结构上确定了具有三角棱柱几何形状的六聚[Ti 6 F 27 ] 3–阴离子。[C（NH 2）3 ] 4 [H 3 O] 4 [Ti 4 F 20 ] [TiF 5 ]的晶体结构确定4显示了混合阴离子全氟钛酸（IV）化合物的第一个实例，该化合物包含两种不同的全氟钛酸（IV）阴离子，即低聚[Ti 4 F 20 ] 4–和一维聚合（[TiF 5 ] –）∞阴离子。还报道了二氟化氢胍胍盐[C（NH 2）3 ] [HF 2 ]的晶体结构。
更新日期：2018-12-17
中文翻译：
胍基全氟钛酸（IV）化合物：低聚[Ti6F27] 3-阴离子的结构测定，以及包含两种不同氟钛酸（IV）阴离子的混合阴离子盐的实例
研究了碳酸胍或氯化胍与四氟化钛在无水氟化氢（aHF）中的化学反应。将获得的产物从饱和的HF，SO 2和CH 3 CN溶液中重结晶。单晶生长导致检测到七种全氟钛酸盐（IV）化合物，这些化合物具有结构特征。其中三个对应于在aHF中作为合成主要产物而获得的相，即[C（NH 2）3 ] 2 [TiF 6 ]，[C（NH 2）3 ] 4 [Ti 4 F 20 ]，和[C（NH 2）3] [Ti 2 F 9 ]。当胍盐/ TiF 4摩尔比大于1：2时，所得产物仅微溶于aHF或完全不溶于aHF。因此，尝试使用其他非质子传递溶剂（SO 2和CH 3 CN）进行单晶生长。在前者和[C（NH 2）3 ] 4 [H 3 O] 4 [Ti 4 F 20 ]的情况下，检测到[C（NH 2）3 ] 3 [Ti 6 F 27 ] · SO 2单晶。在后者的情况下为[TiF 5 ] 4。[H 3 O] +的存在可以用在超酸aHF中质子化的痕量H 2 O污染来解释。形成副产物[H 5 O 2 ] 4 [Ti 8 F 36 ]和β-[H 3 O] [Ti 2 F 9 ]的原因相同。新的胍基全氟钛酸酯（IV）化合物的晶体结构由低聚的[Ti 4 F 20 ] 4–，[Ti 6 F 27 ]组成3–和[Ti 8 F 36 ] 4–以及聚合（[TiF 5 ] –）∞和（[Ti 2 F 9 ] –）∞全氟钛酸（IV）阴离子。首次在结构上确定了具有三角棱柱几何形状的六聚[Ti 6 F 27 ] 3–阴离子。[C（NH 2）3 ] 4 [H 3 O] 4 [Ti 4 F 20 ] [TiF 5 ]的晶体结构确定4显示了混合阴离子全氟钛酸（IV）化合物的第一个实例，该化合物包含两种不同的全氟钛酸（IV）阴离子，即低聚[Ti 4 F 20 ] 4–和一维聚合（[TiF 5 ] –）∞阴离子。还报道了二氟化氢胍胍盐[C（NH 2）3 ] [HF 2 ]的晶体结构。
京公网安备 11010802027423号