Synthesis,Characterization and Properties of Transition Metal Pd/Pt [60]Fullerene Complexes Containing Phosphate Ligands-Crystal Structure of [Pd(eta~2-C_(60)){Ph_2PCH_2(CH_2OCH_2)_2CH_2PPh_2}]

摘要

A solution of C_(60) in toluene reacts with Pd(dba)_2 or Pd_2(dba)_3 (dba=dibenzylideneacetone) and monophosphanes in a 1:1:1 molar ratio to give the corresponding Pd monophosphane fullerene derivatives [Pd(eta~2-C_(60)L_2][L=P(2-Fu)_3 (Fu=furyl) 1;L=P(2-Fu)Ph_2 2;L=PPh_2H 3;L=P(Fc)Ph_2(Fc=ferrocenyl) 4;L=P(Fc)_2Ph 5],whereas reaction with M(dba)_2 (M=Pd,Pt) and subsequent treatment with diphosphanes in 1:1:1 molar ratio afforded the corresponding Pd/Pt diphosphane fullerene complexes [Pd(eta~2-C_(60){Ph_2PCH_2(CH_2-OCH_2)_nCH_2PPh_2}] (n=1,6;n=27;n=38) and [Pt(eta~2-C_(60)-{Ph_2PCH_2(CH_2OCH_2)_nCH_2PPh_2}](n=19;n=2 10;n=3 11).All the new fullerene complexes 1-11 were characterized by elemental analysis,IR,~1H NMR and ~(31)P NMR spectroscopy,as well as by X-ray diffraction analysis (for 7).The optical limiting properties of 3-5 were determined and the possible pathways for the "one pot" reactions leading to 1-11 are briefly discussed.