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New insight into role of ortho-metallation in rhodium triphenylphosphite complexes. Hydrogen mobility in hydrogenation and isomerization of unsaturated substrates.
Autorzy
Rok wydania
2000
Czasopismo
Journal of Organometallic Chemistry
Numer woluminu
597
Strony
69-76
DOI
10.1016/S0022-328X(99)00594-X
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
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.
Słowa kluczowe
Rhodium complexes, ortho-Metallation, Triarylphosphite, Hydrogenation, Isomerization
Adres publiczny
https://doi.org/10.1016/S0022-328X(99)00594-X
Strona internetowa wydawcy
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