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À propos de : Pd-(MOP) Chemistry: Novel Bonding Modes andInteresting Charge Distribution        

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  • Pd-(MOP) Chemistry: Novel Bonding Modes andInteresting Charge Distribution
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  • New Pd-MOP acetyl acetonate complexes, [Pd(acac)(10a)]BF4, 12a (10a = (R)-2-(diphenylphosphino)-2‘-methoxy-1,1‘-binaphthyl), and [Pd(acac)(11-H)], 13 (11 = 2-(R)-(diphenylphosphino)-2‘-hyroxy-1,1‘-binaphthyl), were prepared. X-ray diffraction methods reveal that both structures contain Pd−C σ-bonds arising from the MOP naphthyl backbone. In structure 13, the hydroxyl function in 11 has lost a proton to afford a keto-anionic chelating ligand. 13C NMR studies confirm the solid-state structures.
  • The new Pd-MOP acetyl acetonate complexes [Pd(acac)(10a or 10b)]BF4, 12a,b, wereprepared starting from [Pd(acac)(CH3CN)2]BF4, whereas [Pd(acac)(11-H)], 13, was obtaineddirectly from Pd(acac)2 by adding 11. [Ligand 10a, MeO-MOP = (R)-2-(diphenylphosphino)-2‘-methoxy-1,1‘-binaphthyl; ligand 11, HO-MOP = (R)-2-(diphenylphosphino)-2‘-hydroxy-1,1‘-binaphthyl]. The solid-state structures for cationic 12a and neutral 13 were determinedvia X-ray diffraction methods and reveal that both structures contain Pd−C σ-bonds arisingfrom the MOP naphthyl backbone. In structure 13, the hydroxyl function in 11 has lost aproton to afford a keto-anionic chelating ligand. 13C NMR studies confirm that the solutionstructures are the same as those found in the solid state and, for 12, describe how the organiccation distributes the positive charge.
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