Abstract
The reduction of dichlorotris(triphenylphosphine)ruthenium(II) in tetrahydrofuran–acetonitrile by sodium or magnesium amalgam produces a compound shown to be a hydrido ortho-metallated phosphine ruthenium(II) complex RuH(C6H4PPh2)(MeCN)(PPh3)2. This compound has all the characteristics of a complex previously reported and alleged to be a ruthenium(0) complex containing a π-bonded acetonitrile ‘Ru(MeCN)(PPh3)4·MeCN’.Detailed study of the system shows that there are labile intermediates, Ru(MeCN)2(PPh3)2 which is paramagnetic, Ru(MeCN)3(PPh3)2, and Ru(MeCN)(PPh3)3. The reduction in pyridine gives two isomers of RuH(C6H4PPh2)(C5H5N)(PPh3)2 while in the presence of 2,2′-bipyridyl the main product is a purple complex RuH(C6H4PPh2)(bipy)(PPh3). In styrene the known complex Ru(styrene)2(PPh3)2 is obtained.Reactions of the ruthenium(II) species RuH(C6H4PPh2)(MeCN)(PPh3)2 with propene and water are reported.The various compounds have been characterised by i.r. and 1H and 31P n.m.r. spectroscopy.It is concluded that reductions of RuCl2(PPh3)3 or 4 lead to the abstraction of hydride from the solvent if no strongly co-ordinating ligand is present. In the presence of co-ordinating ligands, species containing ortho-metallated triphenylphosphine groups are formed via intramolecular oxidative addition of a C–H bond to transient ruthenium(0) intermediates.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
