American Chemical Society
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Pd-(MOP) Chemistry:  Novel Bonding Modes and Interesting Charge Distribution

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journal contribution
posted on 2003-12-08, 00:00 authored by Pascal Dotta, P. G. Anil Kumar, Paul S. Pregosin, Alberto Albinati, Silvia Rizzato
The new Pd-MOP acetyl acetonate complexes [Pd(acac)(10a or 10b)]BF4, 12a,b, were prepared starting from [Pd(acac)(CH3CN)2]BF4, whereas [Pd(acac)(11-H)], 13, was obtained directly 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 determined via X-ray diffraction methods and 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 that the solution structures are the same as those found in the solid state and, for 12, describe how the organic cation distributes the positive charge.