Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo‐D_2d Distorted Face‐Capped Pd₁₄ Cubic Kernel: [(μ₁₄‐M)Pd₂₂(CO)₂₀(PEt₃)₈]⁺ (M=Au, Ag)

Abstract

Heart of gold (or silver): The pseudo-D2d distorted MPd14 cubic kernel of [(μ14-M)Pd22(CO)20(PEt3)8](+) cations, with M = Au (1), Ag (2), has an encapsulated M atom (see picture; yellow) coordinated to eight cubic corner (black) and six face-capping Pd atoms (gray). Compounds 1 and 2 were obtained (28-60 % yields) from two-step/one-pot reactions of a Pd10 precursor with CF3CO2 H followed by coinage-metal ion exchange of protons.

Discrete Silver(I)‐Palladium(II)‐Oxo Nanoclusters, {Ag4Pd13} and {Ag5Pd15}, and the Role of Metal–Metal Bonding Induced by Cation Confinement

“…It is noteworthy that, to date, only one nanosized cluster containing Ag–Pd interactions has been structurally characterized, which is supported by organic ligands and is air‐sensitive . To our knowledge, this is the first time that air‐ and light‐stable Ag‐Pd clusters are reported in a fully inorganic system.…”

“…It is noteworthy that, to date,o nly one nanosized cluster containing Ag-Pd interactions has been structurally characterized, which is supported by organic ligands and is airsensitive. [14] To our knowledge,t his is the first time that airand light-stable Ag-Pd clusters are reported in af ully inorganic system. Thec ore structure of both polyanions can be viewed as an onion-like multi-shell assembly,w ith symmetrical cages of different size arranged within each other, resembling aR ussian "Matryoshka" doll with exposed silver attachments ( Figure S3).…”