Dithiotropolonates. II. Synthesis and properties of dithiotropolone and its metal(II) complexes
Dithiotropolonates. II. Synthesis and properties of dithiotropolone and its metal(II) complexes
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二硫代托酚酸盐。
DOI：
10.1021/ja00711a016
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发表时间：
1970
期刊：
影响因子：
--
通讯作者：
R. H. Holm
中科院分区：
文献类型：
--
作者：
C. E. Forbes;R. H. Holm
二硫代酚酮（15）已在约。通过氢硫离子与四氟硼酸1，2-二乙氧基托品酯（13）反应，从托酚酮得到30%的产率，并分离为深红色、空气敏感的晶体。红外，电子和质谱表征数据的报告。托吡酯类化合物13已被证明是合成1，7-二取代1，3，5-环庚三烯的潜在有价值的中间体。与伯胺单独反应和与硫氢化物反应，分别以40-75%的产率产生N-二取代氨基托酮亚胺（16，17）和N-取代氨基硫代托酮（18）。二硫杂环庚三烯酚酮或其钠盐易于与二价金属盐反应，得到一系列颜色强烈、微溶的双螯合物M-（SST）2（7，8）。可能的基态电子结构的这些配合物进行了讨论有关中性双（二硫杂环戊烯）配合物（1）。光谱和极谱研究表明，与二硫代戊烯一样，M（SST）2物种（M=
Dithiotropolone (15) has been prepared in ca. 30% yield from tropolone via thereaction of hydro-sulfide ion with 1, 2-diethoxytropylium tetrafluoroborate (13) and isolated as deep red, air-sensitive crystals. Infrared, electronic, and mass spectral characterization data are reported. The tropylium species 13 has been shown to be a potentially valuable intermediate in the synthesis of 1, 7-disubstituted 1, 3, 5-cycloheptatrienes. Reactions with primary amines alone and with hydrosulfide yield,-disubstituted aminotroponeimines (16, 17) and N-substituted aminothiotropones (18), respectively, in 40-75% yield. Dithiotropolone or its sodium salt readily reacts with divalent metal salts to afford a series of intensely colored, slightly soluble bis-chelate complexes, M-(SST) 2 (7, 8). Probable ground-state electronic structures of these complexes are discussed in relation to neutral bis (dithiolene) complexes (1). Spectral and polarographic studies reveal that, like the dithiolenes, M (SST) 2 species (M=