新型有机配合物Ni(diphos)(CO)_2的合成及其对苯的光羰化反应

SYNTHESIS OF NOVEL ORGANOTRANSITION METAL COMPLEXES Ni(diphos)(CO)_2 AND STUDIES ON ACTIVATION AND FUNCTIONALIZATION OF C-H BOND BY THESE COMPLEXES

通过Ｎｉ（ｄｉｐｈｏｓ）Ｃｌ２在ＣＯ气氛下被Ｎａ（Ｈｇ）还原，合成了４种新型Ｎｉ（ｄｉｐｈｏｓ）（ＣＯ）２配合物，其中ｄｉｐｈｏｓ：ｄＣｙｐＰｅ，ｄＣｙｈＰｅ，Ｐｈ（ｔ－Ｂｕ）Ｐｅ，ＰＰ。这４种配合物均通过红外光谱和元素分析等方法确认。利用上述合成的新型Ｎｉ的双羰基双膦配合物在室温和常压下，成功地进行了苯的光羰化反应性能研究，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，光反应与Ｒｈ（ｄｉｐｈｏｓ）（ＣＯ）Ｃｌ配合物一样都具有较高的选择性。此外，对光羰化反应的机理作了探索。

Four novel Ni(diphos)(CO)_2 complexes have been synthesized from the reductive reaction of Ni(diphos)Cl_2 using sodium amalgam under carbon monoxide atmosphere at room temperature (diphos: dC ypPe, dC yhPe, Ph(tBu)Pe, [LJ1*6,H,W(1,6,3,4)][JJ2,X,2;5,YS;3,YX] PP ). All the four complexes have been characterized by IR spectra and elemental analysis. The photochemical carbonylations of benzene catalyzed by these novel nickel carbonyl diphosphine complexes have not reported in the literature before. The reaction products (benzaldehyde and benzyl alcohol) were identified by the gas chromatographmass spectrometry. Results showed that these photochemical carbonylations of benzene had the same high catalytic selectivity as those of Rh(diphos)(CO)Cl complexes. Besides, the mechanism of photochemical carbonylation of benzene has been suggested.