851368-19-9Relevant academic research and scientific papers
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.
Single component cationic palladium proinitiators for the latent polymerization of cycloolefins
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Page/Page column 16, (2010/02/13)
Palladium compound compositions are provided in accordance with Formulae [((R)3E)aPd(Q)(LB)b]p [WCA]r, where ((R)3E) is a Group 15 electron donor ligand, Q is an anionic ligand, LB is a Lewis base, WCA is a weakly coordinating anion, a is 1, 2 or 3, b is 0, 1 or 2, the sum of a and b is 1, 2 or 3 and each of p and r is an integer such that the molecular charge is zero, or [(E(R)3)(E(R)2R*)Pd(LB)]p[WCA]r where E(R)2R* represents a Group 15 neutral electron donor ligand and where R* is an anionic hydrocarbyl containing moiety, bonded to the Pd and having a β hydrogen with respect to the Pd center. Such compound composition exhibits latent polymerization activity in the presence of polycyclic olefins.
