Heterometallic palladium-copper and palladium-nickel complexes with pivalate bridges

Pd/Cu-Catalyzed Dehydrogenative Coupling of Dimethyl Phthalate: Synchrotron Radiation Sheds Light on the Cu Cycle Mechanism

“…The potential mechanism involves an acetato group transfer through the "Pd(μ 2 -OAc)Cu" species. It is noteworthy that a related "Pd( 24 To study the re-oxidation step of the monovalent Cu species to a divalent species, the monovalent complex 2c was refluxed for 1.5 h in AcOH in air. Pleasingly, [Cu(OAc) 2 ] 2 •2AcOH (2a• AcOH) was selectively obtained as blue cubic crystals in 90% yield.…”

“…The potential mechanism involves an acetato group transfer through the “Pd­(μ 2 -OAc)­Cu” species. It is noteworthy that a related “Pd­(μ 2 -O 2 C t Bu)­Cu” complex [ trans -(picoline) 2 Pd­(O 2 C t Bu-μ 2 -Pd,Cu) 2 Cu 2 (O 2 C t Bu-μ 2 -Cu,Cu′) 4 ] has been isolated …”

Computational study on palladium-catalyzed alkenylation of remote δ-C(sp3)–H bonds with alkynes: a new understanding of mechanistic insight and origins of site-selectivity

“…Yu et al proposed and Houk et al computationally showed that some C–H bond functionalizations prefer to take place via heterodimeric metal species compared to homodimeric metal species such as PdAg-(OAc) 3 versus Pd 2 (OAc) 4 . 16 Illuminated by these closely relevant precedents and the fact that Ni–Pd(OAc) 4 species has similar dimeric structure with Pd 2 (OAc) 4 , 20 we envisioned that heterodimeric Ni–Pd(OAc) 4 could be utilized to complete the catalytic cycle in a manner like dimeric Pd 2 (OAc) 4 catalyst. The computational results are given in Fig.…”