1338487-75-4Relevant academic research and scientific papers
Hydrogenolysis of palladium(II) hydroxide, phenoxide, and alkoxide complexes
Fulmer, Gregory R.,Herndon, Alexandra N.,Kaminsky, Werner,Kemp, Richard A.,Goldberg, Karen I.
, p. 17713 - 17726 (2011)
A series of pincer (tBuPCP)Pd(II)-OR complexes ( tBuPCP = 2,6-bis(CH2PtBu2)C 6H3, R = H, CH3, C6H5, CH2C(CH3)3, CH2CH2F, CH2CHF2, CH2CF3) were synthesized to explore the generality of hydrogenolysis reactions of palladium-oxygen bonds. Hydrogenolysis of the Pd hydroxide complex to generate the Pd hydride complex and water was shown to be inhibited by formation of a water-bridged, hydrogen-bonded Pd(II) hydroxide dimer. The Pd alkoxide and aryloxide complexes exhibited more diverse reactivity. Depending on the characteristics of the -OR ligand (steric bulk, electron-donating ability, and/or the presence of β-hydrogen atoms), hydrogenolysis was complicated by hydrolysis by adventitious water, a lack of reactivity with hydrogen, or a competing dissociative β-hydride abstraction reaction pathway. Full selectivity for hydrogenolysis was observed with the partially fluorinated Pd(II) 2-fluoroethoxide complex. The wide range of Pd-OR substrates examined helps to clarify the variety of reaction pathways available to late-transition-metal alkoxides as well as the conditions necessary to tune the reactivity to hydrogenolysis, hydrolysis, or dissociative β-hydride abstraction.
