851368-19-9Relevant articles and documents
Reactivity studies of cationic palladium(II) phosphine carboxylate complexes with lewis bases: Substitution versus cyclometalation
Thirupathi, Natesan,Amoroso, Dino,Bell, Andrew,Protasiewicz, John D.
, p. 3157 - 3166 (2007)
Two classes of cationic palladium(II) phosphine carboxylate complexes were isolated and characterized. Reactions of trans-[(R3P) 2Pd(O2CR′)2] (1) with [Li(OEt 2)2.5][B(C6F5)4] in MeCN led to carboxylate abstraction and formation of trans-[(R3P) 2Pd(O2CR′)(MeCN)][B(C6F5) 4] (2) in good to excellent yields. On the other hand, carboxylate abstraction reactions of 1 with [Me2(H)NPh][B(C6F 5)4] or p-toluenesulfonic acid (HOTs·H 2O) in CH2Cl2 furnished the palladium cations [(R3P)2Pd(κ2-O,O-O2CR′)] + (3). The reactions of 2 and 3 with Lewis bases were found to be different in some cases. For example, reactions of 2 with pyridine furnished the simple products of acetonitrile substitution, trans-[(R3P) 2Pd(O2CR′)(py)][B(C6F5) 4]. In contrast, the reaction of 3e (R = iPr, R′ = CH3) with CD3CN in the presence of excess sodium carbonate yielded a material derived from cyclometalation of one of the iPr arms of iPr3P ligand. New complexes were characterized by elemental analyses and NMR (1H, 13C, and 31P) spectroscopic methods and in two cases by single-crystal X-ray structural methods.
