Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/63740
Title: Reactions of MH(OTf)(NBD)(PPh3)2 (M = Ru Os) with H2
Authors: Lo, ST
Xu, Z
Wen, TB
Ng, WS
Liu, SH
Zhou, ZY
Lin, Z
Lau, CP
Jia, G
Issue Date: 2000
Publisher: American Chemical Society
Source: Organometallics, 2000, v. 19, no. 22, p. 4523-4530 How to cite?
Journal: Organometallics 
Abstract: Treatment of RuHCl(NBD)(PPh3)2 (NBD = norbornadiene) with AgOTf produced RuH(OTf)(NBD)(PPh3)2. Reaction of RuH(OTf)(NBD)(PPh3)2 with H2 in benzene gave norbornene and [(η6-C6H6)RuH(PPh3)2]OTf. The same reaction in CD2Cl2 in the presence of added PPh3 produced norbornane and [RuH(PPh3)4]OTf. Reaction of OsH3Cl(PPh3)3 with norbornadiene produced OsHCl(NBD)(PPh3)2, which was converted to OsH(OTf)(NBD)(PPh3)2 on treatment with AgOTf. Reaction of OsH(OTf)(NBD)(PPh3)2 with H2 in benzene gave norbornane and [(η6-C6H6)OsH(PPh3)2]OTf. In dichloromethane, OsH(OTf)(NBD)(PPh3)2 reacted with H2 in the presence of added PPh3 to produce norbornane and [OsH3(PPh3)4]OTf. Supported by computational studies, it is assumed that the dihydrogen complexes [MH(H2)(NBD)(PPh3)2]+ (M = Ru, Os) were involved in the hydrogenation reactions. Two reaction pathways for the conversion of [RuH(H2)(NBD)(PH3)2]+ to [RuH(NBE)(PH3)2]+ (NBE = norbornene) have been studied by density functional theory calculations. The results show that the first hydrogen transferred to the olefin ligand is more likely from the hydride ligand rather than from the dihydrogen ligand.
URI: http://hdl.handle.net/10397/63740
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om000369x
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