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首页> 外文期刊>Organometallics >Thermochemical investigation of phosphine ligand substitution reactions involving trans-(PR3)(2)Cl2Ru = CH-CH = CPh2 complexes
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Thermochemical investigation of phosphine ligand substitution reactions involving trans-(PR3)(2)Cl2Ru = CH-CH = CPh2 complexes

机译：涉及反式（PR3）（2）Cl2Ru = CH-CH = CPh2配合物的膦配体取代反应的热化学研究

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The enthalpies of reaction of (PPh3)(2)Cl2Ru=CH-CH=CPh2 (1) with a series of tertiary phosphine ligands, leading to the formation of (PR3)(2)Cl2Ru=CH-CH=CPh2 complexes (PR3 = (PPr3)-Pr-i, PBz(3), PPh2Cy, PPhCy2, PCy3, and (PBu3)-Bu-i) have been measured, by solution calorimetry in CH2Cl2 at 30 degrees C. The range of reaction enthalpies spans some 6.5 kcal/mol and helps to establish a relative order of complex stability for,these six ruthenium carbene complexes. The enthalpies of reaction for tertiary phosphine complexes, trans-(PR3)(2)Cl2Ru=CH-CH=CPh2, are as follows (PR3, kcal/mol): PPh3, 0; PBz(3), -1.3 (0.2); PCyPh2, -1.8 (0.2); PCy2Ph, -3.8 (0.2); (PBu3)-Bu-i, -3.8 (0.2); (PPr3)-Pr-i, -5.2 (0.1); PCy3, -6.5 (0.3). The thermodynamics of the exchange of these sterically demanding tertiary phosphine-ligands for PPh3 in 1 provides a measurement of the relative importance of phosphine steric and electronic properties/character to the enthalpy of reaction in this system. Correlations of various factors gauging the electron-donating properties of the phosphine ligands clearly show the electronic factor to be the overwhelming contributor to the enthalpy of reaction in this system. [References: 48]
机译：（PPh3）（2）Cl2Ru = CH-CH = CPh2（1）与一系列叔膦配体的反应焓，导致形成（PR3）（2）Cl2Ru = CH-CH = CPh2复合物（PR3 =通过在30°C的CH2Cl2中进行溶液量热法测量了（PPr3）-Pr-1，PBz（3），PPh2Cy，PPhCy2，PCy3和（PBu3）-Bu-i）。 6.5 kcal / mol，有助于为这六个钌卡宾配合物建立相对稳定的相对顺序。反式-（PR3）（2）Cl2Ru = CH-CH = CPh2的叔膦配合物的反应焓如下（PR3，kcal / mol）：PPh3，0; PBz（3），-1.3（0.2）; PCyPh2，-1.8（0.2）; PCy2Ph，-3.8（0.2）; （PBu3）-Bu-i，-3.8（0.2）; （PPr3）-Pr-i，-5.2（0.1）; PCy3，-6.5（0.3）。这些空间需求的叔膦配体在1中交换为PPh3的热力学提供了该体系中膦的空间和电子性质/特征对反应焓的相对重要性的度量。测量该膦配体的电子给体性质的各种因素的相关性清楚地表明，该电子因素是该系统中反应焓的压倒性贡献者。 [参考：48]

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