by X-ray crystallography. 5 gives two products:  trans-[PtPhMe(PMe2Ph)2] and trans-[PtPh2(PMe2Ph)2]. Steric effects on the reactivity speak in favor of an associative mechanism. The surprisingly high reactivity for the transmetalations, compared to the substitution reactions, can be explained in terms of an associative mechanism, where a strong, bridging Sn−F interaction stabilizes the transition state
                                    合成了反式-[PtPhFL 2 ]类型的配合物,其中L = PPh 3(4),PMe 2 Ph(5)。配合物4通过X射线晶体学表征。的平衡常数的
氟化物反式的取代苯基在4经Cl -和我-被确定,并且稳定性序列遵循在“软”
金属中心看到的正常的趋势:即,
铂具有用于卤化物中的偏好顺序I> Cl> F; 但是,差别很小。取代动力学遵循通常的二项速率定律,并且溶剂分解的速率常数(k 1)和直接(ķ 2测定)反应途径为ķ 1 =(9.7±2.4)×10 - 5个小号- 1,ķ 2 =(11.7±0.3)×10 - 2中号- 1个小号- 1和ķ 1 =(7.1±4.9)×10 - 5小号- 1,ķ 2 =(23.0±1.3)×10 - 2中号- 1个小号- 1为
氯-和我-, 分别。对于有Cl的溶剂化和直接途径激活参数-如传入
配体是典型的关联过程和被确定为Δ ħ ⧧ = 77.8±5.5千焦耳摩尔- 1,Δ小号⧧