单核零价过渡金属配合物的研究——Ⅰ.含有π-键合配体与双齿膦配体(dppm、dppe)的混合配体零价钯配合物的合成与表征

STUDY ON MONONUCLEAR ZERO-VALENT TRANSITION METAL COMPLEXES——Ⅰ.SYNTHESIS AND CHARACTERIZATION OF MIXED-LIGAND Pd(O)COMPLEXES CONTAINING π-BONDING LIGANDS AND BIDENTATE PHOSPHINE LIGANDS(dppm,dppe)

本文利用逐级配体取代反应,合成了一系列六个含有 dppm、dppe 的混合配体零价钯配合物,[(L_2)pd(L_2′)](L_2′分别为双苄叉酮(PhCH=CHCOCH=CHPh,dba),2,3,5,6,-四氟-1,4-对苯醌(PQ)和2,3-二氯-1,4-对萘醌(PnQ);L_2分别为 dppm(dppm=Ph_2PCH_2CH_2PPh_2),dppe(dppe=Ph_2PCH_2 CH_2PPh_2)]。通过元素分析、红外光谱,电子光谱以及′H-NMR 和^(31)P-NMR 谱对这些配合物进行了表征。结果表明 dppm 和 dppe在这些配合物中都起双齿配体的作用,二者的配位行为相同。配体 dba,PQ 和 PnQ分别利用其-C=C-双键与 Pd 原子进行配位。

A series of mixed-ligand Pd(O)complexes(L_2)Pd(L_′2) [L′_2 =PhCH=CHCOCH=CHPh(dba).2.3.5.6-tetrachloro-1.4-benzoquinone(PQ) and 2.3-dichloro-1.4-naphthoquinone(PnQ).respectively:L_2=Ph_2PCH_2PPh_2(dppm)and Ph_2PCH_2CH_2PPh_2(dppe)respectively]were synthesized by the reaction of step-by-step ligand substitution.These complexes were characterized through elemental analyses.IR spectra,electronic spectra.~1H-NMR and ~31P-NMR spectra.The results showed that both dppm and dppe behaved as bidentate ligands and the same way of coordination,and they also showed that ligands dba.PQ and PnQ were coordinated on to the Pd atom through their C=C moiety.