Addition of carbon nucleophiles to the allenylidene ligand of [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4: synthesis of new organic ligands by formal C−C coupling between mutually inert fragments
Addition of carbon nucleophiles to the allenylidene ligand of [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4: synthesis of new organic ligands by formal C−C coupling between mutually inert fragments
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将碳亲核试剂添加到 [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4 的丙二烯配体上：通过互惰性片段之间的正式 C−C 偶联合成新的有机配体
DOI：
10.1021/om9708539
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发表时间：
1997
期刊：
影响因子：
--
通讯作者：
E. Oñate
中科院分区：
文献类型：
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作者：
Miguel A. Esteruelas;A. Gómez;Ana M. López;A. Modrego;E. Oñate
对模型阳离子[Ru(η5-C5H5)(CCCH2)(CO)(PH3)]+ (1a)的EHT-MO计算表明，[Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4(1)的LUMO和HOMO分别占23%和31%和26%，分别位于烯基配体的Cα、Cγ和Cβ上。在这些结果的基础上，我们报道了一种新的合成策略，用于制备由苯乙炔、丙酮和甲烷正式加成到1的烯丙二烯的化合物。用LiC - CPh处理1会生成烯基络合物Ru(η5-C5H5){C(C - CPh)CCPh2}(CO)(PiPr3)(2)和炔基衍生物Ru(η5-C5H5){C -C -C (Ph)2C - CPh}(CO)(PiPr3)(3)。2与HBF4反应生成取代的碳化合物[Ru(η5-C5H5){C(C) CPh)CHCPh2}(CO)(PiPr3)]BF4(4)，这是由苯乙炔在1的丙烯二烯的Cα−Cβ双键上正式加成而成。用x射线晶体学测定了4的分子结构。钌中心周围的几何结构接近于八面体，具有环戊二烯链。
EHT-MO Calculations on the model cation [Ru(η5-C5H5)(CCCH2)(CO)(PH3)]+ (1a) suggest that 23% and 31% of the LUMO and 26% of the HOMO of [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4 (1) are located on Cα, Cγ, and Cβ of the allenylidene ligand, respectively. On the basis of these results, we report a new synthetic strategy for the preparation of compounds resulting from the formal addition of phenylacetylene, acetone, and methane to the allenylidene of 1. Treatment of 1 with LiC⋮CPh leads to the allenyl complex Ru(η5-C5H5){C(C⋮CPh)CCPh2}(CO)(PiPr3) (2) and the alkynyl derivative Ru(η5-C5H5){C⋮C−C(Ph)2C⋮CPh}(CO)(PiPr3) (3). The reaction of 2 with HBF4 affords the substituted carbene compound [Ru(η5-C5H5){C(C⋮CPh)CHCPh2}(CO)(PiPr3)]BF4 (4), which is a result from the formal addition of phenylacetylene to the Cα−Cβ double bond of the allenylidene of 1. The molecular structure of 4 has been determined by X-ray crystallography. The geometry around the ruthenium center is close to octahedral with the cyclopentadienyl liga...