Mononuclear Organometallic Platinum(II) Complexes and Platinum(II)−Copper(I) Mixed Complexes from Symmetrical 3,5-Bis(iminoacetyl)pyrazolate Ligands

The reaction of symmetrical dinucleating ligands 3,5-bis(4-methoxyphenyliminoacetyl)-4-methylpyrazole (bmimpH, 1a) and 3,5-bis(2,6-dimethylphenyliminoacetyl)-4-methylpyrazole (bdmimpH, 1b) with [(μ-Me2S)PtMe2]2 or (Me2S)2PtPh2 affords selectively mononuclear complexes LPtMe(SMe2) or LPtPh(SMe2) (L = bmimp, bdmimp). Reaction of these complexes with CuCl gives access to ionic compounds {[LPtMe(SMe2)]2Cu+CuCl2− and [LPtPh(SMe2)]2Cu+CuCl2−, which exhibit dynamic behavior in solution for L = bdmimp. Ligand deprotonation followed by reaction with (Me2S)2PtPh2 affords mononuclear anionic complexes K+[LPtPh2]−. These react with CuCl to give dimeric structures of formula {[LPtPh2]2Cu2}, which exhibit Pt→Cu dative bonds and a CuCu contact, and dynamic behavior in solution.

对称双核配位配体3,5-双(4-甲氧基苯基亚氨基乙酰基)-4-甲基吡唑(3,5-bis(4-methoxyphenyliminoacetyl)-4-methylpyrazole, 缩写bmimpH, 1a)与3,5-双(2,6-二甲基苯基亚氨基乙酰基)-4-甲基吡唑(3,5-bis(2,6-dimethylphenyliminoacetyl)-4-methylpyrazole, 缩写bdmimpH, 1b)，分别与[(μ-二甲基硫)二甲基合铂(II)]二聚体[(μ-Me₂S)PtMe₂]₂或二(二甲基硫)二苯基合铂(II)(Me₂S)₂PtPh₂反应，可选择性生成单核配合物LPtMe(SMe₂)或LPtPh(SMe₂)（L代表bmimp、bdmimp）。上述单核配合物与氯化亚铜(CuCl)反应，可得到离子型化合物{[LPtMe(SMe₂)]₂Cu⁺CuCl₂⁻}与{[LPtPh(SMe₂)]₂Cu⁺CuCl₂⁻}；当L为bdmimp时，该类化合物在溶液中表现出动态行为。将上述配体脱质子后，再与二(二甲基硫)二苯基合铂(II)(Me₂S)₂PtPh₂反应，可得到单核阴离子配合物K⁺[LPtPh₂]⁻。该类阴离子配合物与CuCl反应，生成通式为{[LPtPh₂]₂Cu₂}的二聚体结构，该结构中存在Pt→Cu配位键与Cu-Cu相互作用，且在溶液中同样表现出动态行为。