Carbon-Sulfur Bond Cleavage Reactions of Quinolyl-Substituted Thiophenes with Iron Carbonyls
Carbon-Sulfur Bond Cleavage Reactions of Quinolyl-Substituted Thiophenes with Iron Carbonyls
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喹啉取代的噻吩与羰基铁的碳硫键断裂反应
DOI：
10.1021/acs.organomet.7b00280
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发表时间：
2017
期刊：
影响因子：
2.8
通讯作者：
Masakazu Hirotsu
中科院分区：
文献类型：
--
作者：
Takumi Matsunaga;Isamu Kinoshita;Masakazu Hirotsu
喹啉取代噻吩的热反应（2-（8′-喹啉基）噻吩（QT），2-甲基-5-（8′-喹啉基）噻吩（MeQT），2-（8′-喹啉基）-5-（三甲基硅基）噻吩（TMSQT）与[Fe_3（CO）_（12）]反应，得到相应的硫醇桥联二铁配合物[Fe_2（μ-LR）（CO）_5]（R = H、Me、SiMe 3），其中LH、LMe和LTMS分别是通过QT、MeQT和TMSQT中的C-S键的氧化加成形成的双阴离子N、C、S-三齿配体（SC（R）CHCHC（Q）2-，Q = 8-喹啉基）。相反，喹啉取代噻吩与[Fe（CO）5]的光反应产物的形成依赖于噻吩环上的R基团。QT的光反应生成无硫的二铁配合物[Fe 2 {CHCHCHC（Q）}（CO）5]，而MeQT和TMSQT的光反应分别生成硫醇根桥联的三铁配合物[Fe 3（μ-LMe）（CO）8]和二铁配合物[Fe 2（μ-LTMS）（CO）5]。在三铁配合物[Fe_3（μ-LR）（CO）_8]中，Fe（CO）_3单元与二铁配合物[Fe_2（μ-LR）（CO）_5]中S-金属配体的C（R）CHCH部分结合。根据硫醇盐配合物[Fe_2（μ-LR）（CO）_5]和[Fe_3（μ-LR）（CO）_8]的反应性，描述了光反应产物的差异。虽然二铁配合物[Fe 2（μ-LR）（CO）5]与[Fe（CO）5]的光反应产生相应的三铁配合物[Fe 3（μ-LR）（CO）8]，但对于R = H，导致形成[Fe 2 {CHCHCHC（Q）}（CO）5]的脱硫是主要的，并且对于R = SiMe 3，观察到三铁配合物快速转化为CO消除产物。
Thermal reactions of quinolyl-substituted thiophenes (2-(8′-quinolyl)thiophene (QT), 2-methyl-5-(8′-quinolyl)thiophene (MeQT), 2-(8′-quinolyl)-5-(trimethylsilyl)thiophene (TMSQT)) with [Fe3(CO)12] gave the corresponding thiolate-bridged diiron complexes [Fe2(μ-LR)(CO)5] (R = H, Me, SiMe3), where LH, LMe, and LTMSare dianionic N,C,S-tridentate ligands (SC(R)CHCHC(Q)2–, Q = 8-quinolyl) formed by the oxidative addition of the C–S bond in QT, MeQT, and TMSQT, respectively. In contrast, the formation of photoreaction products of the quinolyl-substituted thiophenes with [Fe(CO)5] was dependent on the R group of the thiophene ring. The photoreaction of QT gave the sulfur-free diiron complex [Fe2{CHCHCHC(Q)}(CO)5], whereas the photoreactions of MeQT and TMSQT gave the thiolate-bridged triiron complex [Fe3(μ-LMe)(CO)8] and diiron complex [Fe2(μ-LTMS)(CO)5], respectively, as the major products. In the triiron complexes [Fe3(μ-LR)(CO)8], an Fe(CO)3unit is bound to the C(R)CHCH moiety in the S-metallacycle of the diiron complexes [Fe2(μ-LR)(CO)5]. The difference in the photoreaction products is described on the basis of the reactivity of the thiolate complexes [Fe2(μ-LR)(CO)5] and [Fe3(μ-LR)(CO)8]. Although the photoreactions of the diiron complexes [Fe2(μ-LR)(CO)5] with [Fe(CO)5] produced the corresponding triiron complexes [Fe3(μ-LR)(CO)8], desulfurization leading to the formation of [Fe2{CHCHCHC(Q)}(CO)5] was predominant for R = H, and a fast conversion of the triiron complex to a CO elimination product was observed for R = SiMe3.