INTRODUCTION OF A FUNCTIONAL ORGANIC MOLECULE INTO FERROCENYLENE BRIDGED DINUCLEAR PLATINUM COMPLEXES

为了开发将功能有机分子引入二茂铁桥接双核铂配合物的方法，研究了1,1′-二茂铁二基二铂配合物{C_5H_4Pt(COD)Cl]_2Fe(1)的COD-或Cl-配体交换反应。配合物(1)与1,5 -二（二苯基膦）戊烷或1,6 -二（二苯基膦）己烷在二甲基二硫化物存在下进行环二烯-配体交换反应，形成甲基硫代桥接的1,1′-二茂铁二基二铂配合物（mu-SMe）{(C_5H_4PtCl)2{Ph_2P(CH_2)_nPPh_2}Fe(2)，其中铂原子被二膦配体桥接。二膦桥接配合物与非桥接单齿三膦类似物（mu-SMe）{C_5H_4Pt(PAr_3)Cl]_2Fe(3)具有相似的电子能谱、NMR和CD等物理性质。铜催化配合物(1)与7个末端乙炔的烷基化反应得到烷基化产物{C_5H_4Pt(COD)XICCR]_2Fe(4a, b.c)， R=Ph， 1-萘基，二茂铁。与- pt - cxic -桥接的二茂铁三聚体（4c）的CV数据表明，二茂铁基团之间的相互作用较弱。与二膦的配合物Ph_2P(CH_2)_nPPh_2 （n=1,2,3）进行配体交换反应，得到顺式螯合二膦衍生物{C_5H_4Pt(Ph_2P(CH_2)_nPPh_2)Cl]_2Fe (5a, b, c) (n=1,2,3)，其中Cp环与铂配位面之间的二面角按n数顺序增大。在这种情况下，电子谱中dpi-siguma*的λ damax和CV中的El/2等物理性质根据n数逐步变化。配合物5c的α - h和α - h共振峰在室温下呈聚并峰。

In order to develop introducing methods of a functional organic molecule into the ferrocenylene-bridged dinuclear platinum complexes, COD- or Cl- ligand exchange reactions of 1,1'-ferrocenediyldiplatinum complex {C_5H_4Pt(COD)Cl]_2Fe(1) have been investigated.The cyclooctadiene-ligand exchange reaction of the complex (1) with 1 , 5-bis(diphenylphosphino)pentane or 1 , 6-bis(diphenylphosphino)hexane in the presence of dimethyldisulfide results in the formation of methylthiolato-bridged 1,1 '-ferrocenediyldiplatinum complexes (mu-SMe){(C_5H_4PtCl)2{Ph_2P(CH_2)_nPPh_2}Fe(2) in which platinum atoms are bridged by the diphosphine ligand. The diphosphine-bridged complexes show similar physical properties, such as electronic spectra, NMR and CD to those of the nonbridged monodentate triaryiphosphine analog, (mu-SMe){ C_5H_4Pt(PAr_3)Cl]_2Fe(3).The Cu-catalyzed alkynylation of the complex (1) with seven terminal acetylene affords the alkynyl products {C_5H_4Pt(COD)XICCR]_2Fe(4a, b.c), R=Ph, 1-naphthyl, ferrocenyl. The CV dataof the ferrocene trimer(4c) bridged with -Pt-CXIC- suggests that the interactions between the ferrocene groups are weak.The COD-ligand exchange reaction of the complexes with diphosphines Ph_2P(CH_2)_nPPh_2 (n=1,2,3 ) affords cis-chelated diphosphine derivatives {C_5H_4Pt(Ph_2P(CH_2)_nPPh_2)Cl]_2Fe (5a, b, c) (n=1,2,3) of which the dihedral angle between the Cp ring and the coordinate-plane of platinum increases in order of n-number. In this case, physical properties such as lambdamax of dpi-siguma* in electronic spectra and El/2 in CV, change stepwise according to n-number. The beta- and alpha-H rssonance peaks of complex 5c show a coalesced peak at room temperature in ^1H NMR.