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

研究了1，1‘-二茂铁二基双铂配合物[C_5H_4PT(COD)Cl]_2Fe(1)与1，5-二(二苯基膦)戊烷或1，5-二(二苯基膦)戊烷的环辛二烯-配体交换反应。在二甲基二硫醚存在下，6-二(二苯基膦)己烷形成了甲硫醇桥联的1，1‘-二茂铁二基双铂配合物(mu-SMe){(C_5H_4PtCl)2{Ph_2P(CH_2)_nPPh_2}Fe(2)，其中铂原子通过双膦配体桥联。双膦桥联化合物的电子光谱、核磁共振和环糊精性质与非桥联三芳基膦类似物(MU-SME){C_5H_4PT(PAR_3)Cl]_2Fe(3)相似，铜催化的化合物(1)与七端乙炔的烷基化反应得到了炔基产物{C_5H_4PT(COD)XICCR]_2Fe(4a，b.c)，R=Ph，1-萘基，二茂铁基。二茂铁三聚体(4c)与二膦配体Ph_2P(CH_2)_nPPh_2(n=1，2，3)的COD-配体交换反应生成顺式络合双膦衍生物{C_5H_4PT(Ph_2P(CH_2)_nPh_2)Cl]_2Fe(5a，b，c)(n=1，2，3)，其中Cp环与铂配位面间的二面角按n-数量级增大。在这种情况下，电子光谱中dpi-siguma*的λmax和CV中的EL/2等物理性质随着n-数的变化而逐步变化。化合物5c的β-和α-H共振峰在~1H核磁共振谱中显示为室温下的聚合峰。

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.