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Low Oxidation State Silicon Clusters – Synthesis and Structure of [NHCDippCu(η4-Si9)]3-

Abstract

The reaction of NHCDippCuCl with the silicide phases A12Si17 (A: K, K/Rb, Rb) in NH3 (l) yields [NHCDippCu(η4-Si9)]3- (1) as the only third example of a substituted [Si9] cluster. The corresponding salts A3[A(2.2.2 crypt)]3[NHCDippCu(η4-Si9)]2·26NH3 (A: K (1a), K/Rb (1b), Rb (1c)) crystallize isostructurally in the space group P-1 and have been characterized by single crystal structure determination. ESI MS and NMR experiments reveal that the anion [NHCDippCu(η4-Si9)]3- can also be transferred to pyridine or acetonitrile solutions at low temperature. However, at room temperature a dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]+-substituted silicide clusters is possible, whereras reactions of K12Si17 with corresponding NHCDippMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M NHC]+, yielding [Si9]3- species.

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Publication details

The article was received on 16 Oct 2017, accepted on 11 Nov 2017 and first published on 13 Nov 2017


Article type: Communication
DOI: 10.1039/C7CC07995H
Citation: Chem. Commun., 2017, Accepted Manuscript
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    Low Oxidation State Silicon Clusters – Synthesis and Structure of [NHCDippCu(η4-Si9)]3-

    F. Geitner and T. F. Fässler, Chem. Commun., 2017, Accepted Manuscript , DOI: 10.1039/C7CC07995H

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