Hydride-encapsulated bimetallic clusters supported by 1,1-dithiolates

Abstract

<p>Two mixed-metal hydride clusters abbreviated as Cu3Ag4H and Cu4Ag3H were structurally characterized from a set of atomically precise heptanuclear clusters, CuxAg7-x(H){S2P(OiPr)2}6 (x = 1-6) synthesized via a one-pot reaction. An...</p>

A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations

“…Presumably, the [M 8 (Cl)L 6 ] + species identified in the gas phase are the decomposition products of M 10 (Se)L 8 in the presence of chloro-solvent. In fact, the observed ion peak distributions for bimetallic clusters are frequently reported in literature [ 25 , 26 , 27 , 28 ].…”

“…Hence, the crystal structure can be best represented as [Cu 3 Ag 7 (Se){Se 2 P(O i Pr) 2 } 8 ] 0.6 [Cu 4 Ag 6 (Se){Se 2 P(O i Pr) 2 } 8 ] 0.4 ([ 3a ] 0.6 [ 3b ] 0.4 ). It is worthwhile to mention that the phenomenon of co-crystallization is frequently observed in heterometallic clusters [ 26 , 27 , 28 , 29 , 30 , 31 ] especially for two heterometals occupying the same site. The copper atoms in M 10 (Se) are distributed in six positions, where two Cu are fully occupied at two brown ellipsoids ( Figure 1 g) and the rest Cu atoms are randomly disordered at four cyan ellipsoids (see Figure S1 ).…”

Intercluster exchanges leading to hydride-centered bimetallic clusters: a multi-NMR, X-ray crystallographic, and DFT study

“…and NaBH4 in a 3:4:6:1 molar ratio. 24 Although both the composition and structure of a hydride-centered bimetallic heptanuclear cluster were unambiguously confirmed by X-ray diffraction, ESI-MS and NMR data from the crystalline products revealed characteristics corresponding to a distribution of hydridecentered bimetallic clusters, CuxAg7-x(H){S2P(O i Pr)2}6 (x = 1 -6), and suggest the occurrence of intramolecular and/or intermolecular metal exchanges both in solution and in the gas phase. Herein we present the inter-cluster reactions (Scheme 1) of 5) and [CuxAg7- Their chemical shifts, line shapes, and relative intensities did not change after 10 minutes, showing that the metal exchange proceeds spontaneously and reaches equilibrium in a very short time.…”

“…Although polyhydrido copper clusters stabilized by chalcogenolates have received tremendous attention due to their potential applications in catalysis, electrocatalytic CO2 reduction, hydrogenation, or energy storage, [20][21][22][23] well-characterized bimetallic hydride clusters of group 11 metals remain scarce partly due to the lack of reliable, convenient synthetic methodologies. [24][25][26] Importantly, the method adopted in this report is significantly different from a recent development by Tsukuda and his co-workers on the subject of hydride-mediated cluster growth involving coinage metals. [27][28]…”

Deep Learning Accelerated Determination of Hydride Locations in Metal Nanoclusters

“…One needs only the right method to uncover this information. The Hirshfeld atom refinement of high‐quality X‐ray data [11] was used to locate the one hydride in Cu x Ag 7− x (H){S 2 P(O i Pr) 2 } 6 clusters; [12] this promising approach of locating hydrides with X‐ray has yet to be used to locate multiple hydrides (>10) in large clusters. Here, we report a novel approach to predict the hydride locations in metal nanoclusters by deep learning [13] .…”