Anion Templated Synthesis of Silver(I)-Ethynide Dithiophosphate Clusters

Abstract

Reaction of AgCC t Bu with (EtO)2PS2Na at room temperature leads to the isolation of two new silver­(I)-ethynide compounds incorporating the dithiophosphate ligand, namely, {CO3@(Ag3)4(CC t Bu)4(EtO)2PS2]6}·0.5H2O (1) and {(CO3)2@Ag26(CC t Bu)16[(EtO)2PS2]4}·2­(OH)·4MeOH·6H2O (2). Besides, we obtain another three silver­(I)-ethynide clusters S@Ag11(CC t Bu)2[(EtO)2PS2]7 (3), {S@Ag14(CCPh)8[(EtO)2PS2]4(TMEDA)2}·5MeOH (4), and {S@Ag14(CCPh)8[( i PrO)2PS2]4(TMEDA)2}·7CH3OH (5), with AgCCR (R= t Bu, Ph) and (RO)2PS2Na (R= Et, i Pr) as the starting materials. Complexes 1–2 are templated by a carbonate anion in situ generated from the fixation of atmospheric CO2 in a basic TMEDA-containing solution, and TMEDA can also lead to the disassembly of dithiophosphate to give a sulfide ion as the template for the generation of 3–5.

Tetrahedral Geometry Induction of Stable Ag–Ti Nanoclusters by Flexible Trifurcate TiL3 Metalloligand

“…Within the core of PTC-87 lies a tetrahedral SO 4 2– anion which may act as a template for this structure. The sulfate oxygen atoms point in the direction of each triangular face of the truncated tetrahedrons. − Each hexagonal face of the truncated tetrahedron hosts three 2-propanethiolate anions to give a total of 12 2-propanethiolate anions. According to XPS analysis (Figure S13), Ag atoms in PTC-87 also show valence states of +1, which is in agreement with those in [SO 4 @Ag 22 ( i PrS) 12 (NO 3 ) 6 ·2NO 3 ] n …”

Trivalent Tetrahedral Anion Template: A 26-Nucleus Silver Alkynyl Cluster Encapsulating Vanadate

“…The template approach has been widely used in the fabrication of molecular assemblies. − In the literature, a chemical template has been introduced as an organizer of the assembly of atoms in the molecule. , The reports indicate that anion templates have a determinative role in the features of the cluster complexes. , The physical properties of the template anions are key factors of the template-directed molecular assemblies . All kinds of anions with different sizes and shapes ,− from the smallest anion like hydride to bigger ones like polyoxometalates, even an organic anion like the squarate dianion, can be encapsulated in the silver cages. In the work of Liu et al, for example, encapsulation of the spherical anions with different sizes and charges led to the preparation of M 8 L 6 clusters (M = Cu I , Ag I ; L = dichalcogeno ligand) with three distinct structures .…”

Serendipitous and Targeted Synthesis of High Nuclearity Clusters—Carbonate and Oxalate Encapsulating Silver Alkynides

“…Q.-M. Wang and co-workers also observed carbonate encapsulation forming heptadeca- and nonadecanuclear silver clusters, depending on the employed counterion . Similarly, atmospheric CO 2 trapping into silver alkynide clusters was observed by Lu and co-workers . The structure is highly irregular and has very little resemblance to the polymeric material, but is dominated by various short carbonate- O -Ag (2.260(5) to 2.578(5) Å and water- O -Ag interactions (2.169(5) to 2.387(5) Å) at the center of the cluster.…”