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American Chemical Society, Organometallics, 20(21), p. 4281-4292, 2002

DOI: 10.1021/om020521q

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

Journal article published in 2002 by Sh Liu, Sm Ng, Tb Wen ORCID, Zy Zhou, Zy Lin, Cp Lau, Gc Jia
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This paper is available in a repository.

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Abstract

Treatment of [RuCl(PPh3)(PCP)] (PCP = 2,6-(Ph2PCH2)(2)C6H3) With norbornadiene (NBD,) in the presence of CuCl produces [RuCl(NBD)(PCP)]. Reaction of [RuCl(NBD)(PCP)1 with TlOTf gives [Ru(OTf)(NBD)(PCP)], which reacts with NaBH4 to produce [RuH(NBD)(PCP)]. Protonation of [RuH(NBD)(PCP)l with acetic acid in the presence of PPh3 gives norbornene and [Ru(OAc)(PPh3)(PCP)]. Protonation of [RuH(NBD)(PCP)] with HOTf gives norbornene and [Ru(OTf)(NBD)(PCP)]. Protonation of [RuH(NBD)(PCP)l with HOTf in the presence of MeCN gives norbornene, [Ru(MeCN)(NBD)(PCP)]OTf, and [Ru(MeCN)3(PCP)]OTf. In the protonation reactions, the NBD is likely hydrogenated through the dihydrogen intermediate [Ru(H-2)(NBD)(PCP)](+). A computational study shows that hydrogen transfer from the dihydrogen to the NBD ligand of [Ru(H-2)(NBD)(PCP)](+) proceeds through a stepwise mechanism. ; Department of Applied Biology and Chemical Technology