25966-20-5Relevant academic research and scientific papers
Activation of ortho carbon-hydrogen bonds in triphenyl phosphite complexes
Barefield,Parshall
, p. 964 - 967 (1972)
Interactions between the central rhodium and ligand C-H bonds leading to exchange of hydrogen for deuterium have been observed in [(C6H5O)3P]3RhCl and [(C6H5O)3P]4Rh+. In [(C6H5O)3P]4Rh+ this exchange is preceded by oxidative addition of hydrogen and an equilibrium loss of a proton. Reaction of [(C6H5O)3P]3RhCl with phenylmagnesium chloride produces an air-sensitive ortho-bonded complex [(C6H5O)3P]2(C6H 5O)2POC6H4Rh. Reactions of this complex with H2, DCl, CO, and excess (C6H5O)3P are reported.
New insight into role of ortho-metallation in rhodium triphenylphosphite complexes. Hydrogen mobility in hydrogenation and isomerization of unsaturated substrates
Trzeciak, Anna M.,Ziólkowski, Józef J.
, p. 69 - 76 (2007/10/03)
The hydrogen transfer from two rhodium(I) hydrido complexes HRh{P(OPh)3}4 and HRh(CO){P(OPh)3}3 to methyl acrylate and/or allylbenzene leads to the formation of ortho-metallated complexes Rh{P(OC6H4)(OPh)2}{P(OPh)3} 3 (I) and Rh{P(OC6H4)(OPh)2}(CO){P(OPh)3} 2 (II), respectively. During these reactions unsaturated substrates, methyl acrylate or allylbenzene undergo stoichiometric hydrogenation. A similar reaction was also observed for HRh{P(OR)3}4 complexes (R=3-CH3C6H4, 4-CH3C6H4). The complex HRh{P(OPh)3}4 catalyses the isomerization of hex-1-ene to hex-2-ene in the absence of H2; however at 1 atm of H2 the formation of hexane is observed. Hydrido complexes of the type HRh{P(OR)3}4 in D2 atmosphere undergo H/D exchange at the ortho position of coordinated triarylphosphite. Deuteration of the ortho protons in complexes with R=Ph, 3,5-(CH3)2C6H3 and 4-CH3C6H4 is total, whereas only one ortho hydrogen is replaced in the case of R=3-CH3C6H4. The formation of an ortho-metallated chelating ring causes a downfield shift in the 1H-NMR signal of one proton from the phenyl ring to δ ca. 8 ppm.
Some reactions of compounds of the type [(diene)RhX]2 (diene = cycloocta-1,5-diene, bicyclo[2.2.1]hepta-2,5-diene; X = Cl, Br) with tertiary phosphines and phosphites
Haines, Linda M.
, p. 1517 - 1520 (2008/10/08)
The reactions of various monodentate ligands with the dimeric compounds [(diene)RhX]2 (diene = C8H12, X = Cl, Br; diene = C7H8, X = Cl) are described. Whereas it has been previously established that a
