Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal–metal interactions has been compared to that of hydrogen bonding (ca. 7–11 kcal mol−1) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)–Cu(I), Ag(I)–Ag(I) and Au(I)–Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au–Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d10–d10 interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d10–d10 interactions. Although the focus of this review is on d10–d10 interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d10–d10 interactions involving metals from other groups (188 references).

/pdf/intramolecular-d10-d10-interactions-in-heterometallic-581tky0doc.pdf

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CO2RR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C2+ products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm-2 at -1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu2-CuN3 clusters which are the optimal sites. This cluster can't exist without the applied potential. The N-doping dispersed the reduced Cun clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu2-CuN3 clusters displayed charge-asymmetric sites which were intensified by CH3* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol. 

https://www.nature.com/articles/s41467-022-29035-8.pdf

Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol

The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-t...

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands.

Selective P-P and P-O-P bond formations through copper-catalyzed aerobic oxidative dehydrogenative couplings of H-phosphonates.

The increasing interest in the supramolecular chemistry of gold(I) compounds is a result of the unusual, for example optical properties, of these substances that are a result of interand intramolecular aurophilic interactions. In turn, the self-assembly is often based on the intermolecular gold– gold interactions. 5] Salts of the tetranuclear bis(triphenylphosphane gold(I))halonium dications A that contain four gold atoms in a distorted tetrahedral arrangement with four relatively short intermolecular Au···Au distances and two longer intramolecular Au···Au distances are unusual compounds of this type, which are only stable in the solid state. The bis(trigoldoxonium) dication B and the bis(tetraauriomethane) complex C are the only other examples with a similar arrangement. Similar to A, complexes B and C were only observed in the solid state and they dissociate in solution because of electrostatic repulsion. A series of other tetranuclear gold(I) clusters that consist of two dinuclear gold(I) complexes in which the four gold atoms lie at the corners of a distorted square is known, for example {[(Ph3PAu)2SCH2Ph]2} 2+ (D). An important class of building blocks for supramolecular gold(I) compounds are Au alkynyl complexes. Coinage-metal clusters can be prepared through the p-coordination of the alkynes to coinage-metal ions in combination with metallophilic interactions. Only a limited number of such coinage-metal clusters that solely consist of gold(I) cations with ethynido/alkyne ligands have been described. Herein we report distorted tetrahedral Au4 clusters with carboranylethynido ligands. These clusters are formed by selfassembly of two dinuclear gold(I) complexes and they are present in the solid sate and for the first time in solution, as well. Cesium ethynylcarba-closo-dodecaborate reacts with [R3PAuCl] and potassium bis(trimethylsilyl)amide in THF to give the neutral dinuclear gold(I) complexes [12-(R3PAu)2C C-closo-1-CB11H11] (R = Me (1), Et (2), iPr (3), tBu (4)) in 63–95% yield and which are thermally stable up to 220 8C (1; Scheme 1).

Tetrahedral Gold(I) Clusters with Carba-closo-dodecaboranylethynido Ligands: [{12-(R3PAu)2CC-closo-1-CB11H11}2]†

Two-dimensional triangular and square heterometallic clusters: influence of the closed-shell d10 electronic configuration.

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d10–d10 Interactions

Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies

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Two-dimensional triangular and square heterometallic clusters: influence of the closed-shell d10 electronic configuration.

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d10–d10 Interactions

Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies