Homoleptic Tetrakis(silyl) Complexes of Pd0 and Pt0 Featuring Metal‐Centred Heterocubane Structures: Evidence for the Existence of the Corresponding Mononuclear PdI and PtI Complexes. Issue 52 (21st November 2013) - Armbruster, Felix
Abstract We report on the first homoleptic tetrakis(silyl) complexes of zerovalent Group 10 metals. The compounds [MLi4{Si(3, 5‐Me2pz)3}4] (M=Pd and Pt; 3, 5‐Me2pz=3, 5‐dimethylpyrazolyl) exhibit very appealing metal‐centred heterocubane structures with the central d10 metal atoms surrounded by four silicon and four lithium atoms. Both compounds were characterised in detail, including X‐ray crystal‐structure analysis and 2D NMR spectroscopic methods such as 7Li, 29Si and 7Li, 195Pt HMQC. Cyclic voltammetry studies, in combination with density functional theory (DFT) calculations, revealed that the corresponding mononuclear cationic d9‐MI and dicationic d8‐MII complexes are accessible by stepwise one‐electron oxidation of the title compounds. Electron paramagnetic resonance (EPR) investigations provided evidence for the existence of the corresponding paramagnetic palladium(I) and platinum(I) complexes.