By R. S. Coffey (auth.), Renato Ugo (eds.)
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Extra info for Aspects of Homogeneous Catalysis: A Series of Advances Volume 1
R. 0M) between -35 0 and 40 DC. There is a statistical distribution of liganded and free triphenylphosphine and tri-p-tolylphosphine within two minutes, so the tri-p-tolylphosphine can be regarded as labelled triphenylphosphine. It can be demonstrated that in the square planar complex, RhCIPa, the three phosphines exchange between cis and trans positions by an intramolecular process faster than the intermolecular exchange between liganded and non liganded phosphine. r. studies and the molecular weight measurements which they have confirmed .
Mixtures of RuCls and triphenylphosphine (optimum ratio Rh: PPhs is 1: 6), RuClz(pPha)4 , RuClz(PPhs)s [51, 137] and [RUZ(PPha)6Cls]Cl. Although RuClz(PPha)s is an active catalyst in benzene [51, 137] it is much more active in the presence of alcohols . g. alcohol, is required to drive the reaction to the right hand side. The true catalyst is RuHC1(PPhs)s which can be prepared via reaction (59) [137-139]. RuClz(PPhs)s + Hz ~ RuHCI(PPhs)s + HCI (59) An X-ray structure shows it has structure VIII with benzene of crystallisation present in the lattice .
The actual product spectrum appears to depend on the halide, the catalyst concentration and is clearly very sensitive to reaction conditions . Attempted hydrogenation of damsin gives isodamsin (52) and in the presence of (52) CH3 o o deuterium gas deuterated isodamsin is formed . 3. CATALYST POISONS Many substances reduce the activity of these catalysts because they oxidise it to a form of rhodium(III) which cannot be reduced by hydrogen under the mild conditions employed. Thus carbontetrachloride and chloroform, give a series of rhodium trichlorides , allyl chloride gives RhClz(C3Hs)(PPh3)2  and acetyl chloride gives RhCI2COCH3(pPh3)2 .