Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes,Advanced Synthesis & Catalysis

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Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2020-04-06 , DOI: 10.1002/adsc.202000166
Jiarui Chang ₁ , Fei Fang ₁ , Jie Zhang ₁ , Xuenian Chen _{1,

2}

Affiliation

Bis(phosphinite) pincer platinum hydride complexes, [2,6‐(R₂PO)₂C₆H₃]PtH (R=^tBu, ⁱPr), were synthesized, characterized and applied to the hydrosilylation of aldehydes and ketones. NMR study and single crystal X‐ray diffraction analysis indicated that the hydrides in these two platinum complexes are comparatively less hydridic: down‐field ¹H NMR resonances (0.71 and 0.98 ppm) and weak Pt−H interactions were observed. Both the platinum complexes were found to be good catalysts for the hydrosilylation of aldehydes and ketones with phenylsilane. The corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the resultant hydrosilylation products and turnover frequencies (TOFs) up to 3200 h⁻¹ were achieved at 60 °C in toluene, which are much higher than those of the hydrosilylation catalysed by the corresponding nickel pincer hydride complexes. A possible mechanism for the present hydrosilylation process was discussed.

中文翻译：

双次膦酸酯夹式氢化铂配合物催化醛和酮的氢化硅烷化

合成了（2,6-（R ₂ PO）₂ C ₆ H ₃ ] PtH（R = ^t Bu，ⁱ Pr）双（次膦酸酯）夹心氢化铂配合物，表征并将其用于醛和酮的氢化硅烷化。NMR研究和单晶X射线衍射分析表明，这两种铂络合物中的氢化物的氢化物相对较少：下场¹观察到H NMR共振（0.71和0.98 ppm）和弱的Pt-H相互作用。发现两种铂配合物都是醛和酮与苯基硅烷进行硅氢加成反应的良好催化剂。在将所得的氢化硅烷化产物进行碱性水解后，可以分离出相应的醇，收率高至优异，并且在60°C的甲苯中达到3200 h ^-1的周转频率（TOF）远高于由苯甲酸酯催化的氢化硅烷化反应相应的氢化镍夹合物。讨论了目前氢化硅烷化方法的可能机理。

更新日期：2020-04-06

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