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本文研究了在[Rh(COD)(dppe)]Cl(COD=1,5-环辛二烯;dppe=Ph_2PCH_2CH_2PPH_2)和CO存在下,甲烷与邻二氯苯之间的H/Cl交换反应,反应的活性物种是一个含羰基和dppe的铑配合物.在trans-PtHL_2X(L=PEt_3,P(n-Pr)_3,P(n-Bu)_3,PPh_3, X=Cl~-,Br~-,I~-,CN~-)配合物存在下的甲烷氧化氯化反应中,配合物的催化活性与叔膦配体的供电性,圆锥角以及阴离子X配体的反位效应有关.此外,还考察了在含双氮螯合配体的铂配合物存在下,乙炔插入甲烷C-H键的反应,在实验和量子化学计算的基础上提出了可能的反应机理.
In this paper, the H / Cl exchange reaction between methane and orthodichlorobenzene in the presence of [Rh (COD) (dppe)] Cl (COD = 1,5-cyclooctadiene; dppe = Ph_2PCH_2CH_2PPH_2) The reactive species was a rhodium complex containing a carbonyl group and dppe, and the catalytic activity of trans-PtHL_2X (L = PEt_3, P (n-Pr) -, I ~ -, CN ~ -) complex, the catalytic activity of the complex is related to the chargeability of the tertiary phosphine ligand, the cone angle, and the anti-site effect of the anionic X ligand. The reaction of acetylene with methane CH bond inserted in the presence of a platinum complex containing a bis-nitrogen chelate ligand was also investigated. Based on the experimental and quantum chemical calculations, the possible reaction mechanism was proposed.