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By M.M. Taqui Khan

Activation Of Small Inorganic Molecules

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The rate of hydrogénation, however, was reduced when thiophenol was added to the catalyst in the ratio of 5:2. The inhibition of the catalytic effect of the rhodium(I) complex may be due to the equilibrium between the normal catalytic species, (PPh 3 ) 3 RhCl, and a thiol complex of rhodium(I), only the former species contributing to the catalytic reaction. In contrast to thiophenol, alkyl and aryl sulfides do not affect the activity of the catalyst. Further study is required to elucidate the nature of the intermediate complexes involved.

8 The oxidative addition of RX to d metal complexes is strongly influenced by steric factors and depends on the size of the neutral ligand L. ,) add a large numbers of molecules [37] such as RCOC1, ROCOC1, CC1 4, and f 71 CH 2 =CH—CH 2 C1, whereas trans-[\TX(CO)L2] (L = PBu Et 2, PBu'Pr , PBu 3 0 adds CH 3 I slowly and does not react with CH 2 =CH—CH 2 C1 or RCOC1 [37]. The σ-donor capacity of the anionic ligand X is also an important factor. The reactivity of the complexes increase with the σ-donor capacity of X in the order CI < Br < I [113].

160] that the RteCR' > RCH—CHR' • R C H 2— C H 2R ' (62) overall rate of reduction of an alkyne is much slower than that of the corresponding alkene. The alkynes studied [110] include phenylacetylene, diphenylacetylene, 3-methyl-l-pentyne-3-ol, 3-methyl-l-bytyne-3-ol, 2-pentyne-l,4-diol, and 1-ethynylcyclohexane-l-ol. Mague and Wilkinson [172] have studied the catalytic properties of tris(triphenylarsine)chlororhodium(I) and tris(triphenylstibine)chlororhodium(I) in the catalytic hydrogénation of alkenes.

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