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首页> 外文期刊>Organometallics >Comparison of the thermal and reductive decarbonylation of a rhodium trifluoroacetyl diphosphine complex
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Comparison of the thermal and reductive decarbonylation of a rhodium trifluoroacetyl diphosphine complex

机译：铑三氟乙酰基二膦配合物的热和还原脱羰作用比较

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摘要

Acyl complexes of rhodium(III) with chelating diphosphine ligands are well known for their stability toward decarbonylation. However, we have found that the corresponding perfluoro complexes do decarbonylate under mild conditions. In this report we address specifically Rh(dppp)(COCF_3)I_2 (dppp = 1,3-bis(diphenylphosphino)propane). Another difference between this compound and rhodium acyl complexes containing monodentate phosphines is that it does not undergo reductive elimination of alkyl halide after decarbonylation. Instead, slow CO dissociation from Rh(dppp)(CO)(CF_3)I_2 occurs to yield Rh(dppp)(CF_3)I_2 as the final product. Reduction of the trifluoroacetyl complex is a net two-electron process that also involves decarbonylation, but through a quite different mechanism. The products consist of Rh(dppp)(CO)I, CF_3~- anion, and iodide. X-ray crystal structures of both Rh(dppp)(COCF_3)I_2 and Rh(dppp)(CF_3)I_2 have been obtained and show the expected square-pyramidal geometry with the acyl/alkyl group in the apical position.
机译：铑（III）与螯合的二膦配体的酰基络合物因其对脱羰基的稳定性而众所周知。但是，我们发现相应的全氟络合物在温和条件下会脱羰基化。在此报告中，我们专门讨论Rh（dppp）（COCF_3）I_2（dppp = 1,3-双（二苯基膦基）丙烷）。该化合物与含单齿膦的铑酰基配合物之间的另一个区别是，脱羰后它不会还原还原卤代烷。取而代之的是，发生了从Rh（dppp）（CO）（CF_3）I_2缓慢释放CO的过程，最终生成了Rh（dppp）（CF_3）I_2。三氟乙酰基络合物的还原是一个纯净的两电子过程，该过程也涉及脱羰作用，但机理却完全不同。产物由Rh（dppp）（CO）I，CF_3〜-阴离子和碘化物组成。已获得Rh（dppp）（COCF_3）I_2和Rh（dppp）（CF_3）I_2的X射线晶体结构，并显示了预期的方形金字塔形几何结构，其中酰基/烷基位于顶端位置。

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