Photochemical Alkyne Insertions into the Iron–Thiocarbonyl Bond of [Fe2(CS)(CO)3(Cp)2]

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• 作者：Fabio Marchetti ; Stefano Zacchini ; Valerio Zanotti
• 刊名：Organometallics
• 出版年：2016
• 出版时间：August 22, 2016
• 年：2016
• 卷：35
• 期：16
• 页码：2630-2637
• 全文大小：475K
• 年卷期：0
• ISSN：1520-6041

文摘

Internal alkynes (RC≡CR) react with [Feb>2b>(CS)(CO)b>3b>(Cp)b>2b>] (<b>1b>), under UV radiation, to give the complexes [Feb>2b>{μ-η¹:η³-C(R)═C(R)C═S}(μ-CO)(CO)(Cp)b>2b>] [R = Et, <b>2ab>; R = Ph, <b>2bb>; R = COb>2b>Me, <b>2cb>], as a result of CO displacement and alkyne insertion into the metal–CS bond of <b>1b>. In addition, the reaction of <b>1b> with EtC≡CEt affords the metallacycle species [Feb>2b>{μ-η²:η²-C(S)C(Et)═C(Et)C(O)}(CO)b>2b>(Cp)b>2b>] (<b>3b>) as secondary product. The molecular structures of <b>2ab> and <b>3b> have been elucidated by X-ray diffraction studies. Compound <b>1b> reacts with HC≡CCOb>2b>Me, affording the complex [Feb>2b>{μ-η¹:η³-C(H)═C(COb>2b>Me)C═S}(μ-CO)(CO)(Cp)b>2b>] (<b>2db>) in modest yield. Complexes <b>2ab>,<b>bb> undergo selective methylation at the sulfur atom, generating the cationic complexes [Feb>2b>{μ-η¹:η³-C(R)═C(R)═C(SMe)}(CO)(μ-CO)(Cp)b>2b>][CFb>3b>SOb>3b>] [R = Et, <b>4ab>; R = Ph, <b>4bb>]. The X-ray structure of <b>4ab> has also been determined. Finally, <b>4bb> undergoes nucleophilic addition of hydride and cyanide (from NaBHb>4b> and NBuⁿb>4b>CN, respectively) to form the vinylalkylidene complexes [Feb>2b>{μ-η¹:η³-C(Ph)C(Ph)═C(X)(SMe)}(CO)(μ-CO)(Cp)b>2b>] [X = H, <b>5b>; X = CN, <b>6b>].