Affiliation:
1. Coordination Chemistry Saarland University Campus C4.1 D‐66123 Saarbrücken Germany
2. Dipartimento di Scienze Chimiche Università degli Studi di Padova via Marzolo 1 Padova I‐35131 Italy
3. Experimental Physics and Center for Biophysics Saarland University Campus E2.9 D‐66123 Saarbrücken Germany
4. Katalyse mit phosphorhaltigen Materialien Leibniz Institut für Katalyse e.V Albert‐Einstein‐Straße 29a D‐18059 Rostock Germany
Abstract
AbstractAtomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic‐ as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross‐Polarization Magic‐Angle Spinning (CP‐MAS) NMR‐, infrared (IR), UV–vis, and X‐ray photoelectron (XP) spectroscopies, single‐crystal X‐Ray diffraction (sc‐XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104‐electron Pd(0) cluster features a cubic Pd8‐core, µ4‐capping phosphinidene ligands, and is air‐stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non‐destructive cluster rearrangement as is required for supramolecular assembly.
Funder
Erasmus+
Deutsche Forschungsgemeinschaft
Horizon 2020 Framework Programme