Novel heterometallic palladium–silver complex

DFT studies on the mechanism of Ag2CO3‐catalyzed hydroazidation of unactivated terminal alkynes with TMS‐N3: An insight into the silver(I) activation mode

“…), which is ascribed to the stronger C–H … O (2.24 and 2.25 Å) and O–H … O (1.79 and 1.80 Å) hydrogen‐bonding interactions and the larger coordination number as compared to the rest structures. Thus, L10 is set as the reference zero‐point of the Gibbs free energy, which agrees well with previous finding that four‐coordinated Ag ion is the optimal . Therefore, the following discussions for stages I and II are, respectively, on the basis of the relative more stable L7 / L8 and L10 to provide HN 3 and vinyl azide.…”

Is silver a mere terminal oxidant in palladium catalyzed C–H bond activation reactions?

“…Although the catalytic attributes of d 8 -d 10 heterobimetallic complexes have only been rarely documented, 29 the crystal structures of related compounds have been reported earlier. 30,31 Interestingly, the number of attempts on the use of pre-designed heterobimetallic homogeneous catalysts has been on a steady increase in recent years. [32][33][34][35] In such heterobimetallic systems, the intermetallic interaction is generally exploited for ne-tuning the catalytic attributes.…”

A steric tethering approach enables palladium-catalysed C–H activation of primary amino alcohols

“…A comprehensive optimization study towards a catalytic reaction revealed a number of key observations: (1) palladium acetate was the optimal catalyst; (2) silver salts were crucial to the success of the reaction; and (3) a commercial gas mixture comprised of 6.25% CO in air and used at a slight positive pressure provided the best results. Although the role of the silver salt may be solely that of a terminal oxidant, it is also possible that it forms a bi-metallic complex with the palladium, which could be important for the observed reactivity 44,45 .…”