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

Abstract

Encouraged by the successful syntheses of alloy nanoclusters (or nanoparticles) via intercluster (or interparticle) reactions, herein we apply this methodology to prepare a series of bimetallic hydride clusters. Mixing of...

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 ].…”

“…Herein we introduced a new strategy, which is inspired by the thermal-induced self-redox reaction of [Ag 7 (H){S 2 P(O i Pr) 2 } 8 ] leading to the generation of a two-electron silver superatom, [Ag 10 {S 2 P(O i Pr) 2 } 8 ] [ 25 ]. In this work, the Se-analogue of [Ag 7 (H){S 2 P(O i Pr) 2 } 8 ] [ 26 ] as precursors under heating ( Scheme 1 b) can yield [Ag 10 (Se){Se 2 P(OEt) 2 }] 8 ( 2 ). The composition of 2 (10 Ag + + 1 Se 2− + 8 dsep ligands) has been characterized by X-ray diffraction, which is the same as 1 but with a completely different solid-state structure.…”

“…Following the same strategy, a diselenophosphate-stabilized bimetallic Cu/Ag hydride, [Cu x Ag 7-x (H){Se 2 P(O i Pr) 2 } 6 ] (x = 1–6) [ 26 ] was used instead of [Ag 7 (H){Se 2 P(O i Pr) 2 } 8 ] ( Scheme 1 c), to form a selenide-centered decanuclear bimetallic cluster, [Cu x Ag 10−x (Se){Se 2 P(O i Pr) 2 } 8 ] (x = 0–7) ( 3 ). This methodology provides a facile route to produce anion-encapsulated heterometallic clusters via a cluster-to-cluster transformation.…”

“…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 ).…”

“…All reactions were carried out under N 2 atmosphere by using standard Schlenk techniques. [Ag 7 (H){Se 2 P(O i Pr) 2 } 6 ] and [Cu x Ag 7-x (H){Se 2 P(O i Pr) 2 } 6 ] (x = 1–6) were prepared by the procedure reported earlier in literature [ 26 ]. 1 H, 31 P and 77 Se NMR spectra were recorded on a Bruker Avance DPX-300 BBO probe spectrometer (Bruker BioSpin, MA, USA), operating at 300.13 MHz for 1 H, 121.49 MHz for 31 P and 57.239 MHz for 77 Se, respectively.…”