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- W2015541547 abstract "The complexes [PdCl 2 (Me 2 RP) 2 ] (R = o-tolyl; α-napthyl) may be isolated in both cis and trans forms. In CHCl 3 solution cis-trans isomerization processes for these complexes are slow and this is ascribed to steric hindrance by the bulky R groups. The cis-trans isomerization is catalyzed by a variety of added ligands L. These isomerization processes have been extensively studied for the complexes cis-and trans-[PdCl 2 (Me 2 o-tolylP) 2 ] in CHCl 3 solution. The results of variable temperature n.m.r. and u.v. kinetic studies are fully consistent with a consecutive displacement mechanism with an ionic species of the type [PdCl(Me 2 o-tolylP) 2 L] + Cl − as an intermediate. The kinetic characteristics are determined by the nature and relative stability of this ionic intermediate. For L = Me 2 o-tolylP the rate of isomerization is zero order in complex and second order in added phosphine concentration. (At 38° k cis →trans = 6.2 × 10 3 l mol −1 s −1 , k trans →cis = 6.3 × 10 3 l mol −1 s −1 ) For L = PPh 3 the rate of isomerization is considerably slower and first order in both complex and added PPh 3 concentrations (k cis →trans 6.3 = × 10 l mol −1 s −1 , k trans →cis = 6.7 × 10 l mol −1 s −1 ). Isomerization is also effected in neat methanol and the rate is first order in complex concentration. N.m.r. studies of mixtures of trans-[PdI 2 (Me 2 o-tolylP) 2 ] and cis-[PdCl 2 (Me 2 o-tolylP) 2 ] in CHCl 3 solution show halogen exchange to occur more rapidly than isomerization. However a cis-diiodo complex is not observed and instead isomerization to the trans-diiodo complex is observed to occur." @default.
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- W2015541547 date "1973-05-15" @default.
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- W2015541547 title "Mechanistic Studies of Isomerization Reactions of Tetragonal Planar Tertiary Phosphine Complexes of Palladium(II)" @default.
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- W2015541547 doi "https://doi.org/10.1139/v73-245" @default.
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