Low oxidation state silicon clusters-synthesis and structure of [NHCDippCu(η4-Si9)]3-

Felix S. Geitner; Thomas F. Fässler

doi:10.1039/c7cc07995h

Low oxidation state silicon clusters-synthesis and structure of [NHC^DippCu(η⁴-Si₉)]^3-

Felix S. Geitner, Thomas F. Fässler

Chair of Inorganic Chemistry with Focus on New Materials

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

The reaction of NHC^DippCuCl with the silicide phases A₁₂Si₁₇ (A: K, K/Rb, Rb) in NH₃(l) yields [NHC^DippCu(η⁴-Si₉)]^3- (1) as only the third example of a substituted [Si₉] cluster. The corresponding salts A₃[A(2.2.2-crypt)]₃[NHC^DippCu(η⁴-Si₉)]₂·26NH₃ (A: K (1a), K/Rb (1b), Rb (1c)) crystallize isostructurally in the space group P1 and have been characterized by single crystal structure determination. ESI-MS and NMR experiments reveal that the anion [NHC^DippCu(η⁴-Si₉)]^3- can also be transferred to pyridine or acetonitrile solutions at low temperature. However, at room temperature dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]⁺-substituted silicide clusters is possible, whereas the reactions of K₁₂Si₁₇ with the corresponding NHC^DippMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M-NHC]⁺, yielding [Si₉]^3- species.

Original language	English
Pages (from-to)	12974-12977
Number of pages	4
Journal	Chemical Communications
Volume	53
Issue number	96
DOIs	https://doi.org/10.1039/c7cc07995h
State	Published - 2017

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@article{3f982328db0941c591eb7247875f3d9b,

title = "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 only the 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 P1 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 dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]+-substituted silicide clusters is possible, whereas the reactions of K12Si17 with the corresponding NHCDippMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M-NHC]+, yielding [Si9]3- species.",

author = "Geitner, \{Felix S.\} and F{\"a}ssler, \{Thomas F.\}",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7cc07995h",

language = "English",

volume = "53",

pages = "12974--12977",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "96",

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TY - JOUR

T1 - Low oxidation state silicon clusters-synthesis and structure of [NHCDippCu(η4-Si9)]3-

AU - Geitner, Felix S.

AU - Fässler, Thomas F.

PY - 2017

Y1 - 2017

N2 - The reaction of NHCDippCuCl with the silicide phases A12Si17 (A: K, K/Rb, Rb) in NH3(l) yields [NHCDippCu(η4-Si9)]3- (1) as only the 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 P1 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 dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]+-substituted silicide clusters is possible, whereas the reactions of K12Si17 with the corresponding NHCDippMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M-NHC]+, yielding [Si9]3- species.

AB - The reaction of NHCDippCuCl with the silicide phases A12Si17 (A: K, K/Rb, Rb) in NH3(l) yields [NHCDippCu(η4-Si9)]3- (1) as only the 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 P1 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 dissociation under the release of the NHC ligand occurs. Variation of the NHC ligand in the [Cu-NHC]+-substituted silicide clusters is possible, whereas the reactions of K12Si17 with the corresponding NHCDippMCl (M: Ag, Au) complexes result in a partial oxidation of the silicide clusters, without attachment of [M-NHC]+, yielding [Si9]3- species.

UR - https://www.scopus.com/pages/publications/85036535374

U2 - 10.1039/c7cc07995h

DO - 10.1039/c7cc07995h

M3 - Article

C2 - 29160873

AN - SCOPUS:85036535374

SN - 1359-7345

VL - 53

SP - 12974

EP - 12977

JO - Chemical Communications

JF - Chemical Communications

IS - 96

ER -

Low oxidation state silicon clusters-synthesis and structure of [NHC^DippCu(η⁴-Si₉)]^3-

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