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)

• Record Type: Journal Article
• Authors: Armbruster, Felix; Augenstein, Timo; Oña‐Burgos, Pascual; Breher, Frank
• Is Part Of: Chemistry. Volume 19:Issue 52(2013)
• Page Start: 17899
• Page End: 17906
• Publication Date: 2013-11-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201303299
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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‐M^I and dicationic d⁸‐M^II 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.</p> </abstract>