| Abstract
| - Protonation of [RuH(NBD)(PCP)] with acetic acid or HOTf leads to the hydrogenation of the NBD ligand. In the protonation reactions, the NBD is likely hydrogenated through the dihydrogen intermediate [Ru(H2)(NBD)(PCP)]+. A computational study shows that hydrogen transfer from the dihydrogen to the NBD ligand of [Ru(H2)(NBD)(PCP)]+ proceeds through a stepwise mechanism.
- 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.
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