Synthesis and Protonation of [RuH(NBD)(2,6-(Ph2PCH2)2C6H3)]

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• 作者：Sheng Hua Liu ; Sze Ming Ng ; Ting Bin Wen ; Zhong Yuan Zhou ; Zhenyang Lin ; Chak Po Lau ; and Guochen Jia
• 刊名：Organometallics
• 出版年：2002
• 出版时间：September 30, 2002
• 年：2002
• 卷：21
• 期：20
• 页码：4281 - 4292
• 全文大小：285K
• 年卷期：v.21,no.20(September 30, 2002)
• ISSN：1520-6041

文摘

Treatment of [RuCl(PPh₃)(PCP)] (PCP = 2,6-(Ph₂PCH₂)₂C₆H₃) with norbornadiene (NBD)in the presence of CuCl produces [RuCl(NBD)(PCP)]. Reaction of [RuCl(NBD)(PCP)] withTlOTf gives [Ru(OTf)(NBD)(PCP)], which reacts with NaBH₄ to produce [RuH(NBD)(PCP)].Protonation of [RuH(NBD)(PCP)] with acetic acid in the presence of PPh₃ gives norborneneand [Ru(OAc)(PPh₃)(PCP)]. Protonation of [RuH(NBD)(PCP)] with HOTf gives norbornaneand [Ru(OTf)(NBD)(PCP)]. Protonation of [RuH(NBD)(PCP)] with HOTf in the presence ofMeCN gives norbornene, [Ru(MeCN)(NBD)(PCP)]OTf, and [Ru(MeCN)₃(PCP)]OTf. In theprotonation reactions, the NBD is likely hydrogenated through the dihydrogen intermediate[Ru(H₂)(NBD)(PCP)]⁺. A computational study shows that hydrogen transfer from thedihydrogen to the NBD ligand of [Ru(H₂)(NBD)(PCP)]⁺ proceeds through a stepwisemechanism.