Reactions of nucleophiles with bis(µ-thiosulphato-S)-bis(dinitrosylferrate)(2–), [Fe2(S2O3)2(NO)4]2–, and of electrophiles with heptanitrosyltri-µ3-thio-tetraferrate(1–), [Fe4S3(NO)7]–: new routes to bis(µ-organothiolato)-bis(dinitrosyliron) complexes [Fe2(SR)2(NO)4] and the crystal and molecular st
Reactions of nucleophiles with bis(µ-thiosulphato-S)-bis(dinitrosylferrate)(2–), [Fe2(S2O3)2(NO)4]2–, and of electrophiles with heptanitrosyltri-µ3-thio-tetraferrate(1–), [Fe4S3(NO)7]–: new routes to bis(µ-organothiolato)-bis(dinitrosyliron) complexes [Fe2(SR)2(NO)4] and the crystal and molecular st
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亲核试剂与双(μ-硫代硫酸根-S)-双(二亚硝基高铁酸盐)(2–)、[Fe2(S2O3)2(NO)4]2– 的反应，以及亲电子试剂与庚亚硝基三-μ3-硫代四铁酸盐(1–) 的反应), [Fe4S3(NO)7]–：双(μ-有机硫醇)-双(二亚硝基铁)配合物[Fe2(SR)2(NO)4]的新途径以及晶体和分子结构
DOI：
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发表时间：
1990
期刊：
影响因子：
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通讯作者：
M. Hursthouse
中科院分区：
文献类型：
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作者：
C. Glidewell;R. Lambert;M. Harman;M. Hursthouse
双(μ-硫代硫酸根-S)-双(二亚硝基高铁酸盐)(2–), Na2[Fe2(S2O3)2(NO)4] 在硫代硫酸钠存在下，在水溶液中与一系列硫醇 RSH [R = 烷基 (C1–C5)、CH2CO2Me、CH2CH2OH 或 2-嘧啶基] 快速反应，生成中性络合物[Fe2(SR)2(NO)4] 产率通常为 50–65%。与硫化钠形成鲁桑红盐和黑盐的混合物，分别为 Na2[Fe2S2(NO)4] 和 Na[Fe4S3(NO)7]，可通过乙醚溶剂萃取轻松分离。后一种盐与四氟硼酸芳烃重氮盐 RN2+BF4– 反应生成相应的双(μ-芳硫醇)-双(二亚硝基铁)络合物 [Fe2(SR)2(NO)4]。 Na[Fe4S3(NO)7] 与 R3O+BF4–（R = Me 或 Et）烷基化产生 [Fe2(SR)2(NO)4]，但与 Me3S+BF4– 或 Me3SO+ BF4– 发生复分解，而不是烷基化，产生 Me3S+（或 Me3SO+）[Fe4S3(NO)7]–。 [SMe3][Fe4S3(NO)7]晶体为三斜晶系，空间群为P，a= 9.655(2)，b= 11.707(3)，c= 8.968(1)A，α= 106.11(2)，β= 91.78(3)，γ= 84.92(2)°，Z= 2：该化合物是阳离子和阴离子之间没有紧密接触的盐。 [SMe3][Fe4S3(NO)7] 中的阴离子还原为更具亲核性的双阴离子，导致烷基化并形成 [Fe2(SMe)2(NO)4]。
Sodium bis(µ-thiosulphato-S)-bis(dinitrosylferrate)(2–), Na2[Fe2(S2O3)2(NO)4], reacts rapidly in aqueous solution with a range of thiols RSH [R = alkyl (C1–C5), CH2CO2Me, CH2CH2OH, or 2-pyrimidinyl] in the presence of sodium thiosulphate to give the neutral complexes [Fe2(SR)2(NO)4] generally in yields of 50–65%. With sodium sulphide a mixture of the Roussin red and black salts, Na2[Fe2S2(NO)4] and Na[Fe4S3(NO)7] respectively, is formed, readily separable by solvent extraction with diethyl ether. The latter salt reacts with arenediazonium tetrafluoroborates RN2+BF4– to yield the corresponding bis(µ-arenethiolato)-bis(dinitrosyliron) complexes [Fe2(SR)2(NO)4]. Alkylation of Na[Fe4S3(NO)7] with R3O+BF4–(R = Me or Et) yields [Fe2(SR)2(NO)4] but with Me3S+BF4– or Me3SO+ BF4– metathesis, rather than alkylation, occurs to provide Me3S+(or Me3SO+)[Fe4S3(NO)7]–. Crystals of [SMe3][Fe4S3(NO)7] are triclinic, with space group P, a= 9.655(2), b= 11.707(3), c= 8.968(1)A, α= 106.11(2), β= 91.78(3), γ= 84.92(2)°, and Z= 2: The compound is a salt with no close contacts between cation and anion. Reduction of the anion in [SMe3][Fe4S3(NO)7] to the more nucleophilic dianion causes alkylation and formation of [Fe2(SMe)2(NO)4].