Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2013 Jul 3;135(26):9636-9. doi: 10.1021/ja404799m. Epub 2013 Jun 24.
Reaction of [Rh(H)(CO)2(BDP)] (BDP = bis(diazaphospholane)) with styrene at low temperatures enables detailed NMR characterization of four- and five-coordinate rhodium alkyl complexes [Rh(styrenyl)(CO)n(BDP)] presumed to be intermediates in rhodium-catalyzed hydroformylation. The five-coordinate acyl complexes [Rh(C(O)styrenyl)(CO)2(BDP)] are also observed and characterized. The equilibrium distribution of these species suggests an inversion of thermodynamic preference for branched vs linear species from the alkyl to the acyl stage.
[Rh(H)(CO)2(BDP)]（BDP=双（二氮杂膦基））与苯乙烯在低温下的反应使我们能够详细地通过 NMR 对假定为铑催化加氢甲酰化反应中间体的四配位和五配位的铑烷基络合物[Rh(styrenyl)(CO)n(BDP)]进行表征。五配位的酰基络合物[Rh(C(O)styrenyl)(CO)2(BDP)]也被观察到并进行了表征。这些物种的平衡分布表明，从烷基到酰基阶段，热力学上对支链和直链产物的偏好发生了反转。
