Transition-metal–carbon bonds. Part 45. Attempts to cyclopalladate some aliphatic oximes, NN-dimethylhydrazones, ketazines, and oxime O-allyl ethers. Crystal structures of [Pd<sub>2</sub>{CH<sub>2</sub>C(CH<sub>3</sub>)<sub>2</sub>C(NOH)CH<sub>3</sub>}<sub>2</sub>Cl<sub>2</sub>] and [Pd{CH<sub>2</sub>C(NNMe<sub>2</sub>)C(CH<sub>3</sub>)<sub>3</sub>}(acac)]
作者:Anthony G. Constable、Walter S. McDonald、Lynne C. Sawkins、Bernard L. Shaw
DOI:10.1039/dt9800001992
日期:——
PMe2Ph, PPh3, or pyridine). The salts [Pd(CH2C(CH3)2C(NOH)CH3}(Ph2PCH2CH2PPh2)](X = l or BPh4) have also been prepared. E-Ethyl t-butyl and E-phenyl t-butyl ketoximes are similarly cyclopalladated, but oximes of other carbonyl compounds, e.g. trimethylacetaldehyde, methyl isopropyl ketone, di-isopropyl ketone, ethyl methyl ketone, or 2-methylcyclohexanone, give dark intractable products. In contrast, methyl
E-甲基叔丁基酮肟,与乙酸钠和Na 2 [PdCl 4 ]在甲醇中的环钯在叔丁基甲基上区域特异性地反应,得到氯桥联的配合物[Pd 2 CH 2 C(CH 3)2 C(NOH)CH 3 } 2 Cl 2 ](1a),已经确定了其晶体结构(参见下文)。制备了相应的溴化物和碘化物配合物,以及通过桥裂反应制备的几种单核物质,例如[[图] OH] CH 3 } X(L)](X = Cl或Br; L = CO, PMe 2 Ph,PPh 3,或吡啶)。盐[加入Pd(CH 2 C(CH 3)2 C(NOH)CH 3 }(PH 2 PCH 2 CH 2 PPH 2)](X = 1或BPH 4)也被制备。Ë乙基叔丁基类似地,环戊二烯酮和E-苯基叔丁基酮肟具有类似的环palpalpalated,但其他羰基化合物的肟,例如三甲基乙醛,甲基异丙基酮,二异丙基酮,乙基甲基酮或2-甲基环己酮,则可得到深色难处理的产物。丁基NN-二甲基hydr与Na