Dehope Alan, Donnadieu Bruno, Bertrand Guy
UCR-CNRS Joint Research Chemistry Laboratory (UMI 2957), Department of Chemistry, University of California, Riverside, CA 92521-0403 (USA).
J Organomet Chem. 2011 Aug 15;696(17):2899-2903. doi: 10.1016/j.jorganchem.2011.03.010.
Stable cyclic bent-allene 1 displaces the chelating ether linkage of the Hoveyda-Grubbs-type ruthenium complex 2 bearing triphenylphosphine. The resulting complex 3 features an unusual cis-arrangement of the phosphine and the cyclic bent-allene, while retaining a distorted square pyramidal geometry around the ruthenium center. Monitoring by (31)P NMR spectroscopy the reaction of cyclic bent-allene 1 with the indenylidene bis(triphenylphosphine)ruthenium dichloride complex 4 allowed for the observation of dissociated triphenylphosphine, and the formation of a ruthenium complex featuring 1 and triphenylphosphine in the desired trans-configuration. However, continued reaction times saw the disappearance of this complex, and after workup complex 5 featuring a cis-arrangement was isolated.
稳定的环状弯曲丙二烯1取代了带有三苯基膦的霍维达-格鲁布斯型钌配合物2的螯合醚键。所得配合物3具有膦和环状弯曲丙二烯不寻常的顺式排列，同时在钌中心周围保留了扭曲的四方锥几何结构。通过³¹P NMR光谱监测环状弯曲丙二烯1与亚茚基双（三苯基膦）钌二氯化物配合物4的反应，可以观察到解离的三苯基膦，并形成了具有所需反式构型的1和三苯基膦的钌配合物。然而，持续的反应时间导致该配合物消失，后处理后分离出具有顺式排列的配合物5。
