Efficient Demetalation of Fischer Alkoxy- and Amino-Biscarbene Complexes of Chromium via CO-Promoted Sulfuration and Selenylation

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• 作者：Zhaoyan Zheng ; Jinzhu Chen ; Ning Luo ; Zhengkun Yu ; Xiuwen Han
• 刊名：Organometallics
• 出版年：2006
• 出版时间：October 23, 2006
• 年：2006
• 卷：25
• 期：22
• 页码：5301 - 5310
• 全文大小：244K
• 年卷期：v.25,no.22(October 23, 2006)
• ISSN：1520-6041

文摘

CO-promoted sulfuration with elemental sulfur and selenylation with elemental selenium of Fischerbiscarbene complexes of chromium have been achieved by means of in-situ-generated SCO and SeCO,efficiently affording thio- and selenocarboxylates. Intramolecular reactivity inversion of the chromiumcarbene carbon bonds (Cr=C) in an alkoxy-alkoxy biscarbene complex was realized by replacement ofthe alkoxy group bonded to the more reactive Cr=C carbon atom with an amino moiety. A strainedcyclobutenyl ring activates the aminocarbene carbon bond, which thus undergoes oxidation, sulfuration,and selenylation under mild conditions. Demetalation of alkynyl, alkenyl, and alkyl Fischer monocarbenecomplexes was also investigated by the same method, from which selenium- or sulfur-insertion complexesand seleno- and thiocarboxylates were obtained.