[Cu₁₃{S₂CNⁿBu₂}₆(acetylide)₄]⁺: A Two‐Electron Superatom

Abstract

The first structurally characterized copper cluster with a Cu13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu13(S2CNnBu2)6(C≡CR)4](PF6) (R=C(O)OMe, C6H4F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ3 fashion, and each of the six square faces is bridged by a dithiolate ligand in μ2,μ2 fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu13 clusters as two‐electron superatoms, that is, a [Cu13]11+ core passivated by ten monoanionic ligands, with an a1 HOMO containing two 1S jellium electrons.

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

“…Over the past decade, through the work of Liu and co-workers, the range of copperdithiocarbamate clusters has expanded greatly including examples containing hydrides [105][106][107][108] and acetylides [109][110][111][112][113] The addition of thiuram disulfide (TDS) to Cu(I) clusters leads to oxidation and the formation of [Cu(S 2 CNR 2 ) 2 ], and the kinetics and mechanism have been studied [104]. Reactions are proposed to proceed via a rapid equilibrium with adducts [Cu(S 2 CNR 2 )(TDS)], which undergo intramolecular electron transfer in a rate-determining step to afford the final Cu(II) complexes.…”

“…Over the past decade, through the work of Liu and co-workers, the range of copperdithiocarbamate clusters has expanded greatly including examples containing hydrides [105][106][107][108] and acetylides [109][110][111][112][113] ], a process that can be reversed with the loss of H 2 upon oxidation by Ce(IV). The removal of one copper and the formation of heptanuclear [Cu 7 H(µ 3 -S 2 CNR 2 ) 6 ] occurs upon further addition of [BH 4 ] − , a transformation reversed upon the addition of Cu(I) sources.…”

“…This then links these three cluster types while also showing how other copper-dithiocarbamate complexes may decompose to copper-sulfides (see later). The hydrides in these Cu28 clusters are sufficiently acidic deprotonate alkynes, and this has been exploited to afford acetylide-containing clusters [109][110][111]. Thus, [Cu28(H)15(μ4-S2CNR2)12] + reacts with terminal alkynes with H2 evolution to give Cu13 clusters [Cu13(μ4-S2CNR2)6(μ3-C≡CR)4] + (Figure 1a), which contain a centred cuboctahedral [Cu13] 11+ core, being identical to that found in face-centred cubic bulk copper [110].…”

“…The hydrides in these Cu28 clusters are sufficiently acidic deprotonate alkynes, and this has been exploited to afford acetylide-containing clusters [109][110][111]. Thus, [Cu28(H)15(μ4-S2CNR2)12] + reacts with terminal alkynes with H2 evolution to give Cu13 clusters [Cu13(μ4-S2CNR2)6(μ3-C≡CR)4] + (Figure 1a), which contain a centred cuboctahedral [Cu13] 11+ core, being identical to that found in face-centred cubic bulk copper [110]. There are two cluster core electrons and thus, unlike other copper-dithiocarbamate clusters discussed to date, they are mixed-valence complexes containing both Cu(I) and Cu(0) centres.…”

Copper clusters are nanoscale materials comprised of a metal core or frame enclosed by a mantle of stabilizing ligands; their exploration offers progress in diverse fields, such as medicine, electronics, and fundamental chemistry as catalysts, reducing agents, corrosion inhibitors, and petroleum sweeteners. When stabilized with dithiocarbamate (DTC) ligands (L), copper clusters show a propensity for reversible hydrogen uptake and a remarkable versatility in size and shape as demonstrated by the facile subs

“…The reversibility of the hydrogen charging-discharging process, its chemical stability, and its high thermal conductivity render the copper-hydride cluster a promising material for applications in energy and transportation fields. The so-called Chinese puzzle ball is only one of many hydride structures that may be produced with varied copper composition, including Cu 6 [13][14][15][16], Cu 7 [17,18], Cu 8 [19][20][21][22], Cu 13 [23], Cu 14 [24,25], Cu 18 [26,27], Cu 20 [25,28,29], Cu 25 [10,30], Cu 29 [31], Cu 32 [32,33], Cu 53 [34], and Cu 61 [35]. Recent work in this fertile field, including the use of copper hydride compounds as catalyst, has been summarized by several authors [36][37][38][39][40][41].…”