By M.M. Taqui Khan
Activation Of Small Inorganic Molecules
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Additional resources for Activation of Small Inorganic Molecules
Pearson and Muir , however, on the basis of the reaction of CH 3 CHBr25 COOC 2 H 5 ( [ a ] D - 6 ° ) with IrCl(CO)(PPh 2 CH 3 ) 2 concluded that there is no inversion of configuration. The product IrCl(CO)(PPh 2 CH 3 ) 2 (CH 3 CH25 COOC 2 H 5 )Br was found to be optically active, H D - 20°. On cleavage 5 with bromine, the original ester was obtained with rotation [a]^ — 4°. Since there was a slight change in the rotation of the final product it was assumed that there should be two retentions or two inversions in the process of addition of the optically active ester to the iridium complex and subsequent cleavage.
This reaction sequence is in accord with the kinetic and 3 2 [ C o ( C N ) 5] " ~ z ± 6 6 [ C o 2 ( C N ) 1 0] - (32) 3 [ C o 2 ( C N ) 1 0] - + H 2 2 [ C o ( C N ) 5H ] - (33) ki equilibrium studies of Burnett et al. . However, it is not possible to distinguish between this reaction sequence and the one proposed by King and Winfield , as described above, since the intermediate species in the two 6 3 alternative mechanisms, [Co 2 (CN) 1 0] ~ and [H 2 Co(CN) 5 ] ~, are considered to be in very low, steady-state concentrations.
On passing nitrogen through a solution of this complex no free triphenylphosphine was detected in solution. Thus it seems that the sixcoordinate ds-dihydrido complex in equilibrium (57) does not contribute significantly to the reaction pathway, if it exists at all. Consequently the most probable equilibrium for formation of the dihydro species is represented by Eq. (59). RhCl(PPh) 3 + H 2 , R h C l ( H ) 2( P P h 3) 3 (59) Benzene solutions of tris(triphenylphosphine)chlororhodium(I) react with 1 9 ethylene to form a bright yellow crystalline complex, RhCl(PPh 3 ) 2 (C 2 H 4 ).