新型有机配合物Rh(diphos)(CO)Cl的合成及其对苯的光羰化反应

SYNTHESIS OF NOVEL ORGANIC COMPLEXES Rh(diphos)(CO)Cl AND PHOTOCHEMICAL CARBONYLATION OF BENZENE CATALYZED BY THESE COMPLEXES

利用［Ｒｈ（ＣＯ）２（μＣｌ）］２与ｄｉｐｈｏｓ反应，合成了３种新型Ｒｈ（ｄｉｐｈｏｓ）（ＣＯ）Ｃｌ配合物，其中ｄｉｐｈｏｓ＝ｄ（ｔＢｕ）Ｐｅ，ｄＣｙｈＰｅ，ｄＣｙｐＰｅ。这３种配合物均通过红外光谱和元素分析等方法测定确认。利用上述合成的新型Ｒｈ的羰基双膦配合物在室温和常压下，首次成功地进行了苯的光羰化反应性能的研究，反应产物苯甲醛和苯甲醇均经色质分析鉴定确认。结果表明，光反应都具有较高的选择性。同时对光羰化反应的机理作了合理的解释。

The three novel Rh(diphos)(CO)Cl complexes have been synthesized from the reaction of [Rh(CO) 2(μ Cl)] 2 with the diphosphines (diphos=d(t Bu)Pe, dC yp Pe, dC yh Pe). All the three complexes have been characterized by IR spectra and elemental analysis. The photochemical carbonylations of benzene catalyzed by these novel rhodium carbonyl diphosphine complexes have been all first investigated under 1.013×10 5 Pa pressure of carbon monoxide at room temperature. The benzaldehyde and benzyl alcohol of the reaction products were identified by the gas chromatograph mass spectrometry. Results showed that these photochemical carbonylations of benzene had high catalytic selectivity. In addition, the hypothetical mechanism of photochemical carbonylation of benzene has been suggested.