Facile Synthesis of Rhodium(III) Porphyrin Silyls by Silicon−Hydrogen Bond Activation with Rhodium(III) Porphyrin Halides and Methyls

Rhodium(III) porphyrin silyls were synthesized in high yields conveniently from the reactions of
rhodium(III) porphyrin halides and methyls with silanes, via silicon−hydrogen bond activation (SiHA)
in solvent-free conditions. Preliminary mechanistic experiments suggested that rhodium(III) porphyrin
chlorides initially formed cationic rhodium(III) species, which then underwent heterolysis to give the
products. On the other hand, rhodium(III) porphyrin methyls underwent either oxidative addition or σ-bond
metathesis to form the products.

三价铑卟啉硅基配合物可在无溶剂条件下，通过硅氢键活化（SiHA）路径，由三价铑卟啉卤化物与三价铑卟啉甲基配合物分别与硅烷反应，以高收率便捷合成。初步机理实验表明，三价铑卟啉氯化物首先生成阳离子铑(III)物种，随后经异裂得到目标产物；而三价铑卟啉甲基配合物则可通过氧化加成或σ键复分解反应生成目标产物。