Phosphine, iridium complex 336 Subject

The fourth chapter gives a comprehensive review about catalyzed hydroamina-tions of carbon carbon multiple bond systems from the beginning of this century to the state-of-the-art today. As was mentioned above, the direct - and whenever possible stereoselective - addition of amines to unsaturated hydrocarbons is one of the shortest routes to produce (chiral) amines. Provided that a catalyst of sufficient activity and stabihty can be found, this heterofunctionalization reaction could compete with classical substitution chemistry and is of high industrial interest. As the authors J. J. Bmnet and D. Neibecker show in their contribution, almost any transition metal salt has been subjected to this reaction and numerous reaction conditions were tested. However, although considerable progress has been made and enantios-electivites of 95% could be reached, all catalytic systems known to date suffer from low activity (TOP < 500 h ) or/and low stability. The most effective systems are represented by some iridium phosphine or cyclopentadienyl samarium complexes. 

Stimulating results achieved in hydrogenation of C=C double bonds with phosphinerhodium complexes led to the application of these compounds for the catalytic reduction of C=0 and C=N double bonds. The present review summarizes the results in this area reported up until now. To give a more complete picture of the subject, some reports on iridium and ruthenium phosphine complex catalysts have been included as well. 

Iridium(I) dithiocarbamate complexes have been the subject of a paper by Duckett and co-workers (1451). Reaction of NaS2CNEt2 with [lr(cod)(p-Cl)]2 gives [lr(S2CNEt2)(cod)] from which a range of carbonyl, phosphine, and phosphite complexes are readily prepared via displacement of the diolefin, some of which exhibit luminescence in fluid solution at room temperature. Benzene solutions of [lr(S2CNEt2) P(OPh)3 2] are unstable and result in slow formation of the ortho-metalated iridium(lll) hydride, [IrH(S2CNEt2) P(0Ph)3 P(0Ph)20CeH4 ] (Eq. 140), characterized by a hydride resonance at 8 -16.02. 

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