| Budget Amount *help |
¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1998: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1997: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Research Abstract |
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.
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