tert-Butyl-Substituted Poly(ferrocenylene persulfides)
tert-Butyl-Substituted Poly(ferrocenylene persulfides)
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叔丁基取代的聚二茂铁过硫化物
DOI：
10.1021/om00023a045
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发表时间：
1994
期刊：
影响因子：
2.8
通讯作者：
T. Rauchfuss
中科院分区：
文献类型：
--
作者：
D. Compton;T. Rauchfuss
三硫杂二茂铁并菲（RC_5H_3）_2FeS_3（其中R = t-Bu，H）是通过将t-Bu取代的二茂铁进行二硫化反应，然后用单质硫处理而制得的。t-BufcS 3以1，3，1 '-异构体的形式获得。该手性化合物在溶液中由于三硫化物带的相对取向而作为构象异构体的1：1混合物存在。如通过1H NMR测量和X射线晶体学所确定的，以1，3，1 '，4'-异构体的形式获得物质（t-Bu）2fcS 3。在用B u ~ P脱硫后，三硫化物转化为聚合物[（RC_5 H_3）_2FeS_2 In，31 P NMR光谱显示其转化为Bu_3PS。这种脱硫的速率随着反应溶剂的极性而增加。GPC测定表明，t-Bu和（t-Bu）2取代的聚合物为多分散体，Mn分别为3700（M_i = 26000）和2400（M_i = 19000）。可溶性亚二茂铁基过硫化物聚合物在两个步骤中进行可逆的电化学氧化，两个步骤之间相隔290 mV。第一氧化电位类似于三硫化物单体的氧化电位，并且被认为对应于交替的Fe中心的氧化。第二次氧化转化剩余的Fe-位点。用LiBHEt 3还原[（t-Bu）zfcSz]n得到（t-Bu）afcSzLi 2，其可以再氧化（12）成聚合物，硫化（Sa）得到三硫化物，和硒化（Sed）得到（t-Bu）2fcSzLi。
The trithiaferrocenophanes (RC5H3)2FeS3 (where R = t-Bu, H) were prepared by dilithiation of the t-Bu-substituted ferrocenes followed by treatment with elemental sulfur. t-BufcS3 was obtained as the 1,3,1'-isomer. This chiral compound exists in solution as a 1:l mixture of conformers by virtue of the relative orientation of the trisulfide strap. The species (t-Bu)2fcS3 was obtained as the 1,3,1',4'-isomer, as established by lH NMR measurements and X-ray crystallography. The trisulfides were converted to the polymers [(RC5H3)2FeS2In upon desulfurization with B u ~ P , which was shown by 31P NMR spectroscopy to be converted to Bu3PS. The rate of this desulfurization increases with the polarity of the reaction solvent. GPC measurements indicated that the t-Bu-and (t-Bu)2-substituted polymers are polydis-perse with Mn = 3700 (M, = 26000) and Mn = 2400 (M, = 19000), respectively. The soluble ferrocenylene persulfide polymers undergo reversible electrochemical oxidation in two steps, separated by 290 mV. The first oxidation potential is similar to that for the trisulfide monomer and is thought to correspond to oxidation of alternating Fe centers. The second oxidation converts the remaining Fe" sites. Reduction of [(t-Bu)zfcSz]n with LiBHEt3 gave (t-Bu)afcSzLi2, which can be reoxidized (12) to the polymer, sulfurized (Sa) to give the trisulfide, and selenized (Sed to give (t-Bu)2fcS&e.