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Kinetic and thermodynamic preferences for the diastereoselective oxidative addition of H2 to trans-Ir(P*R3)2(CO)Cl: Monodentate chiral phosphines may impart exceptional degrees of diastereoselectivity
Shin, Jun Ho,Parkin, Gerard
, p. 7652 - 7653 (2002)
Studies on square planar iridium complexes of the type trans-Ir(P*R3)2(CO)Cl, where P*R3 is PhP[(C5Me4)]2, PhP[Me2C4H6], or PhP[Pri2C4H6], demonstrate that monodentate chiral phosphines impart exceptional degrees of diastereoselectivity in the oxidative addition of H2. Thus, the oxidative addition of H2 to the two faces of the meso isomer (R,S)-trans-Ir(P*R3)2(CO)Cl proceeds with a kinetic diastereoselectivity which exceeds that for related square planar iridium complexes employing bidentate chiral phosphine ligands. Furthermore, the kinetically favored dihydride is not favored thermodynamically, and the magnitude of the inversion of the kinetic and thermodynamic selectivities is greater than has previously been observed using bidentate phosphines. Copyright
