293309-69-0Relevant academic research and scientific papers
Phosphabenzene compounds and their use in hydroformylation
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, (2008/06/13)
Phosphabenzene compounds of the formula (I) where the radicals R1to R13are, independently of one another, hydrogen, COOM, SO3M, NR3X, NR2, OR, COOR or SR (where M=hydrogen, NH4or alkali metal, X=anion, R=hydrogen or C1-C6-alkyl), or C1-C12-alkyl, C6-C12-aryl, C7-C12-aralkyl, C7-C12-alkaryl or C3-C6-heteroaromatics, where the alkyl, aryl, alkaryl and aralkyl radicals may bear the abovementioned radicals as substituents and two or more of the radicals may be joined to form aliphatic or fused-on rings, where at least one of the radicals R4and R8and at least one of the radicals R9and R13is not hydrogen, can be used for preparing hydroformylation catalysts.
Phosphabenzenes as monodentate π-acceptor ligands for rhodium-catalyzed hydroformylation
Breit, Bernhard,Winde, Roland,Mackewitz, Thomas,Paciello, Rocco,Harms, Klaus
, p. 3106 - 3121 (2007/10/03)
A new class of phosphinine/rhodium catalysts for the hydroformylation of terminal and internal alkenes is presented in this study. A series of phosphabenzenes 1-14 has been prepared by condensation of phosphane or tris(trimethylsilyl)phosphane with the corresponding pyrylium salt. Trans[(phosphabenzene)2RhCl(CO)] complexes 21-25 have been prepared and studied spectroscopically and by X-ray crystal-structure analysis, The hydroformylation of oct-1-ene has been used to identify optimal catalyst preformation and reaction conditions. Hydroformylation studies with 15 monophosphabenzenes have been performed. The catalytic performance is dominated by steric influences, with the phosphabenzene 8/rhodium system being the most active catalyst. Turnover frequencies of up to 45370 h-1 for the hydroformylation of oct-1-ene have been determined. In further studies, hydroformylation activity toward more highly substituted alkenes was investigated and compared with the standard industrial triphenylphosphane/rhodium catalyst. The reactivity differences between the phosphabenzene and the triphenylphosphane catalyst increase on going to the more highly substituted alkenes. Even tetra substituted alkenes reacted with the phosphabenzene catalyst, whereas the triphenylphosphane system failed to give any product. In situ pressure NMR experiments have been performed to identify the resting state of the catalyst. A monophosphabenzene complex [(phosphinine 8)Ir(CO)3H] could be detected as the predominant catalyst resting state.
