1486-01-7Relevant articles and documents
Palladium-catalyzed H-D exchange reaction under hydrothermal condition
Matsubara, Seijiro,Yokota, Yutaka,Oshima, Koichiro
, p. 294 - 295 (2004)
Alkenes and alkanes were converted into fully deuterium labelled ones by treatment with palladium on charcoal and deuterium oxide under hydrothermal condition. The simple method to get fully deuterium labelled compounds is easy to apply to various types of organic compounds.
Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes
Specklin, David,Coffinet, Ana?s,Vendier, Laure,Del Rosal, Iker,Dinoi, Chiara,Simonneau, Antoine
, p. 5545 - 5562 (2021)
We have prepared and characterized a series of unprecedented group 6-group 11, N2-bridged, heterobimetallic [ML4(η1-N2)(μ-η1:η1-N2)Au(NHC)]+ complexes (M = Mo, W, L2 = diphosphine) by treatment of trans-[ML4(N2)2] with a cationic gold(I) complex [Au(NHC)]+. The adducts are very labile in solution and in the solid, especially in the case of molybdenum, and decomposition pathways are likely initiated by electron transfers from the zerovalent group 6 atom to gold. Spectroscopic and structural parameters point to the fact that the gold adducts are very similar to Lewis pairs formed out of strong main-group Lewis acids (LA) and low-valent, end-on dinitrogen complexes, with a bent M-N-N-Au motif. To verify how far the analogy goes, we computed the electronic structures of [W(depe)2(η1-N2)(μ-η1:η1-N2)AuNHC]+ (10W+) and [W(depe)2(η1-N2)(μ-η1:η1-N2)B(C6F5)3] (11W). A careful analysis of the frontier orbitals of both compounds shows that a filled orbital resulting from the combination of the π? orbital of the bridging N2 with a d orbital of the group 6 metal overlaps in 10W+ with an empty sd hybrid orbital at gold, whereas in 11W with an sp3 hybrid orbital at boron. The bent N-N-LA arrangement maximizes these interactions, providing a similar level of N2 push-pull activation in the two compounds. In the gold case, the HOMO-2 orbital is further delocalized to the empty carbenic p orbital, and an NBO analysis suggests an important electrostatic component in the μ-N2-[Au(NHC)]+ bond.
Akawie
, p. 243 (1961)
Changes in ligand coordination mode induce bimetallic C-C coupling pathways
Blacquiere, Johanna M.,Boyle, Paul D.,Jackman, Kyle M. K.,Liang, Guangchao,Zimmerman, Paul M.
, p. 3977 - 3991 (2022/03/31)
Carbon-carbon coupling is one of the most powerful tools in the organic synthesis arsenal. Known methodologies primarily exploit monometallic Pd0/PdII catalytic mechanisms to give new C-C bonds. Bimetallic C-C coupling mechanisms that involve a PdI/PdII redox cycle, remain underexplored. Thus, a detailed mechnaistic understanding is imperative for the development of new bimetallic catalysts. Previously, a PdII-Me dimer (1) supported by L1, which has phosphine and 1-azaallyl donor groups, underwent reductive elimination to give ethane, a PdI dimer, a PdII monometallic complex, and Pd black. Herein, a comprehensive experimental and computational study of the reactivity of 1 is presented, which reveals that the versatile coordination chemistry of L1 promotes bimetallic C-C bond formation. The phosphine 1-azaallyl ligand adopts various bridging modes to maintain the bimetallic structure throughout the C-C bond forming mechanism, which involves intramolecular methyl transfer and 1,1-reductive elimination from one of the palladium atoms. The minor byproduct, methane, likely forms through a monometallic intermediate that is sensitive to solvent C-H activation. Overall, the capacity of L1 to adopt different coordination modes promotes the bimetallic C-C coupling channel through pathways that are unattainable with statically-coordinated ligands.
