Magic number metal nanoclusters are atomically precise nanomaterials that have enabled unprecedented insight into structure-property relationships in nanoscience. Thiolates are the most common ligand, binding to the cluster via a staple motif in which only central gold atoms are in the metallic state. The lack of other strongly-bound ligands for nanoclusters with different bonding modes has been a significant limitation in the field. Herein, we report a previously unknown ligand for gold (0) nanoclusters: N-heterocyclic carbenes (NHCs), which feature a robust metal-carbon single bond, and impart high stability to the corresponding gold cluster. The addition of a single NHC to gold nanoclusters results in significantly improved stability and catalytic properties in the electrocatalytic reduction of CO2. By varying the conditions, nature and number of equivalents of the NHC, predominantly or exclusively monosubstituted NHC-functionalized clusters result. Clusters can also be obtained with up to five NHCs, as a mixture of species.

A series of chiral Au13 nanoclusters were synthesized via the direct reduction of achiral dinuclear Au(I) halide complexes ligated by ortho-xylyl–linked bis-N-heterocyclic carbene (NHC) ligands. A broad range of functional...

Herein, we describe the synthesis of a toroidal Au 10 cluster stabilized by N -heterocyclic carbene and halide ligands via reduction of the corresponding NHC–Au–X complexes (X = Cl, Br, I). The significant effect of the halide ligands on the formation, stability, and further conversions of these clusters is presented. While solutions of the chloride derivatives of Au 10 show no change even upon heating, the bromide derivative readily undergoes conversion to form a biicosahedral Au 25 cluster at room temperature. For the iodide derivative, the formation of a significant amount of Au 25 was observed even upon the reduction of NHC–Au–I. The isolated bromide derivative of the Au 25 cluster displays a relatively high ( ca . 15%) photoluminescence quantum yield, attributed to the high rigidity of the cluster, which is enforced by multiple CH−π interactions within the molecular structure. Density functional theory computations are used to characterize the electronic structure and optical absorption of the Au 10 cluster. 13 C-Labeling is employed to assist with characterization of the products and to observe their conversions by NMR spectroscopy.

Inexorably, the environmental persistence and damage caused by polyolefins have become major drawbacks to their continued long-term use. Global shifts in thinking from fossil-fuel to renewable biobased resources have urged researchers to focus their attention on substituting fossil-fuel based polymers with renewable and biodegradable alternatives on an industrial scale. The recent development of biodegradable polyesters from ring opening polymerization (ROP) of bioderived cyclic ester monomers has emerged as a promising new avenue toward this goal. Ever increasing numbers of metal-based initiators have been reported in the literature for the controlled ROP of cyclic esters, in particular for the polymerization of lactide to produce poly(lactic acid) (PLA). PLA has several material weaknesses, which hinder its use as a replacement for commodity plastics. Despite many advances in developing highly active and controlled catalysts for lactide polymerization, no single catalyst system has emerged to replace industrially used catalysts and provide access to PLA materials with improved properties. We reported the first example of indium(III) for the ring opening polymerization of lactide. Since then, indium(III) has emerged as a useful Lewis acid in initiators for the controlled polymerization of lactide and other cyclic esters. In particular, we have developed a large family of chiral dinuclear indium complexes bearing tridentate diaminophenolate ligands and tetradentate salen and salan ligands. Complexes within our tridentate ligand family are highly active initiators for the moderately isoselective living and immortal polymerization of rac-lactide, as well as other cyclic esters. We have shown that subtle steric effects influence aggregation in these systems, with polymerization typically proceeding through a dinuclear propagating species. In addition, profound effects on polymerization activities have been observed for central tertiary versus secondary amine donors in these and other related systems. In contrast, our well-controlled and highly active chiral indium salen systems are more isoselective than the tridentate analogues and polymerize lactide via a mononuclear propagating species. Again, we have noticed that subtle steric and electronic changes to the ligand can influence both polymerization activity and stereoselectivity via aggregation phenomena. Recently, we have reported a promising new chiral indium catalyst supported by a tetradentate salan ligand. This catalyst is remarkably water and air stable and can be activated by linear and branched alcohols to provide controlled access to multiblock copolymers in air. This catalyst represents an important step forward toward generating new, commercially relevant catalysts for ROP of cyclic esters to produce novel biodegradable polymers, and highlights the unique value of indium-based catalysts in the field.

We report a gem-specific homo- and cross-dimerization of terminal alkynes catalyzed by a well-defined iron(II) complex containing Cp* and picolyl N-heterocyclic carbene (NHC) ligands, and featuring a piano-stool structure. This catalytic system requires no additives and is compatible with a broad range of substrates, including those with polar functional groups such as NH and OH.

Functionalized diaminophenols, H(N(R1R2)N(R3)O), were investigated as ligands for indium catalysts in the ring-opening polymerization of racemic lactide. Precursor complexes (N(Me2)N(Me)O)InCl(2) (1), (N(Pr2)NO)InCl(2) (2), and (N(Mes)NO)InCl(2) (3) were synthesized and fully characterized by (1)H and (13)C NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Complexes 1 and 2 were used to synthesize alkoxy-bridged complexes [(N(Me2)N(Me)O)InCl](2)(μ-Cl)(μ-OEt) (4) and [(N(Pr2)NO)InCl](2)(μ-Cl)(μ-OEt) (5). These complexes catalysed the polymerization of racemic lactide at different rates, with complex 5 being substantially more active than complex 4. The dissociation behaviour of these catalysts in the presence of lactide was also studied and used to make comparisons with previously reported catalyst systems.

Magic number metal nanoclusters are atomically precise nanomaterials that have enabled unprecedented insight into structure-property relationships in nanoscience. Thiolates are the most common ligand, binding to the cluster via a staple motif in which only central gold atoms are in the metallic state. The lack of other strongly-bound ligands for nanoclusters with different bonding modes has been a significant limitation in the field. Herein, we report a previously unknown ligand for gold (0) nanoclusters: N-heterocyclic carbenes (NHCs), which feature a robust metal-carbon single bond, and impart high stability to the corresponding gold cluster. The addition of a single NHC to gold nanoclusters results in significantly improved stability and catalytic properties in the electrocatalytic reduction of CO₂. By varying the conditions, nature and number of equivalents of the NHC, predominantly or exclusively monosubstituted NHC-functionalized clusters result. Clusters can also be obtained with up to five NHCs, as a mixture of species.

The synthesis of the first alkoxide-bridged indium complex supported by a chiral dinucleating ligand platform (1), along with its zinc analogue (2), is reported. Both complexes are synthesized in a one-pot reaction starting from a chiral dinucleating bis(diamino)phenolate ligand platform, sodium ethoxide, and respective metal salts. The dinucleating indium analogue (7) based on an achiral ligand backbone is also reported. Indium complexes bearing either the chiral or achiral ligand catalyze the ring-opening polymerization of racemic lactide (rac-LA) to afford highly heterotactic poly(lactic acid) (PLA; Pr > 0.85). The indium complex bearing an achiral ligand affords essentially atactic PLA from meso-LA. The role of the dinucleating ligand structure in catalyst synthesis and polymerization activity is discussed.