Reinterpretation of five recent crystal structures of heteropoly and isopoly complexes: divanadodecamolybdophosphate, trivanadoenneamolybdophosphate, ".gamma.-dodecatungstophosphate", the dodecamolybdate-dodecamolybdomolybdate blue complex, and dihydrogen
Reinterpretation of five recent crystal structures of heteropoly and isopoly complexes: divanadodecamolybdophosphate, trivanadoenneamolybdophosphate, ".gamma.-dodecatungstophosphate", the dodecamolybdate-dodecamolybdomolybdate blue complex, and dihydrogen
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DOI：
10.1021/ic00172a024
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发表时间：
1984-02
影响因子：
4.6
通讯作者：
H. T. Evans;Michael T. Popev
中科院分区：
文献类型：
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作者：
H. T. Evans;Michael T. Popev
当我们中的一个人于1971年发表杂多和同多复杂分子结构的综述时，已经出现了1 25种晶体结构测定，其中只有11种得到了完整的描述。自那时起，已报告了大约 100 个此类测定，其中大多数都是高质量的。这些文献构成了我们理解此类化合物的化学的基础，通常不会出现歧义或不同的解释。然而，正如 Marsh 和 Shoemaker2 最近所表明的那样，晶体结构研究有时确实会陷入程序和解释错误，从而导致重大的化学误解。我们在此提请注意与同多和杂多配合物有关的四项此类有缺陷的研究。二钒十钼钼磷酸盐，3 [PV2Mo10O40] $"，三钒烯钼钼磷酸盐，3 [PVjMt^ O^] 6"，和“7-十二钨磷酸盐”，4 [PWjjO^] 3· 所有这些钨酸盐和 钒钼酸盐配合物被描述为一种类似于Keggin分子的所谓新配合物，但具有更高的八面体对称性和更多的笼形特征，其中P04基团在分子内无序。尽管所描述的钨酸盐配合物的结构尚未得到很好的完善，4但很明显，该分子结构实际上与详细描述的钒钼酸盐配合物中的分子结构相同。 3 我们从后一份报告中的内部证据得出结论，两者均由晶体内完全双重无序的普通 Keggin 分子组成。
When one of us published in 1971 a review of the heteropoly and isopoly complex molecular structures, 1 25 crystal structure determinations had appeared, of which only 11 were com-pletely described. Since then some 100 such determinations have been reported, mostly of high quality. This literature, which forms the foundation for our understanding of the chemistry of this class of compounds, is generally not subject to ambiguity or varying interpretations. However, as Marsh and Shoemaker2 recently showed, occasionally a crystal structure study does fall into errors of procedure and interpretation that can lead to major chemical misunderstanding. We draw attention here to four such flawed studies concerned with isopoly and heteropoly complexes.Divanadodecamolybdophosphate, 3 [PV2Mo10O40] $", Trivanadoenneamolybdophosphate, 3 [PVjMt^ O^] 6", and “7-Dodecatungstophosphate”, 4 [PWjjO^] 3· All of these tungstate and vanadomolybdate complexes are described as a so-called new complex similar to the Keggin molecule but having higher, octahedral symmetry and more clathrate character, with the P04 group in disorder within the molecule. Although the structure of the tungstate complex described is not well refined, 4 it is clear that this molecular structure is virtually identical with that in the vanadomolybdate complexes, which were described in detail. 3 We conclude from internal evidence in the latter report that both consist of an ordinary Keggin molecule in full twofold disorder within the crystal.