Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]–(R = iBu, iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K-18c6)Au[Ge9{Si(iBu)3}3]2, and (K-18c6)2[Ge9{Si(iBu)3}2]

Lorenz J. Schiegerl; Felix S. Geitner; Christina Fischer; Wilhelm Klein; Thomas F. Fässler

doi:10.1002/zaac.201600295

Functionalization of [Ge₉] with Small Silanes:[Ge₉(SiR₃)₃]^–(R = iBu, iPr, Et) and the Structures of (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃], (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂, and (K-18c6)₂[Ge₉{Si(iBu)₃}₂]

Lorenz J. Schiegerl, Felix S. Geitner, Christina Fischer, Wilhelm Klein, Thomas F. Fässler

Chair of Inorganic Chemistry with Focus on New Materials

Technical University of Munich

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

33 Scopus citations

Abstract

Novel silylation reactions at [Ge₉] Zintl clusters starting from the chlorosilanes SiR₃Cl (R = iBu, iPr, Et) and the Zintl phase K₄Ge₉are reported. The formation of the tris-silylated anions [Ge₉(SiR₃)₃]^–[R = iBu (1a), iPr (1b), Et (1c)] by heterogeneous reactions in acetonitrile was monitored by ESI-MS measurements. For R = iBu¹H,¹³C and²⁹Si NMR experiments confirmed the exclusive formation of 1a. Subsequent reactions of 1a with CuNHC^DippCl and Au(PPh₃)Cl result in formation of the neutral metal complex (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃]·0.5 tol (2·0.5 tol) and the metal bridged dimeric unit {Au[Ge₉{Si(iBu)₃}₃]₂}^–(3a), isolated as a (K-18c6)⁺salt in (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂·tol (3·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18-crown-6, crystals of the compound (K-18c6)₂[Ge₉{Si(iBu)₃}₂]·tol (4·tol), containing the bis-silylated cluster anion [Ge₉(Si(iBu)₃)₂]^2–(4a), were obtained. The compounds 2·0.5 tol, 3·tol and 4·tol were characterized by single-crystal structure determination.

Original language	English
Pages (from-to)	1419-1426
Number of pages	8
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	642
Issue number	24
DOIs	https://doi.org/10.1002/zaac.201600295
State	Published - Dec 2016

Keywords

Coinage Metals
Functionalization
Germanium
Silanes
Zintl clusters

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10.1002/zaac.201600295

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Schiegerl, L. J., Geitner, F. S., Fischer, C., Klein, W., & Fässler, T. F. (2016). Functionalization of [Ge₉] with Small Silanes:[Ge₉(SiR₃)₃]^–(R = iBu, iPr, Et) and the Structures of (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃], (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂, and (K-18c6)₂[Ge₉{Si(iBu)₃}₂]. Zeitschrift fur Anorganische und Allgemeine Chemie, 642(24), 1419-1426. https://doi.org/10.1002/zaac.201600295

@article{ff3be57bbd0349b98ba6872a51151e71,

title = "Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]–(R = iBu, iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K-18c6)Au[Ge9{Si(iBu)3}3]2, and (K-18c6)2[Ge9{Si(iBu)3}2]",

abstract = "Novel silylation reactions at [Ge9] Zintl clusters starting from the chlorosilanes SiR3Cl (R = iBu, iPr, Et) and the Zintl phase K4Ge9are reported. The formation of the tris-silylated anions [Ge9(SiR3)3]–[R = iBu (1a), iPr (1b), Et (1c)] by heterogeneous reactions in acetonitrile was monitored by ESI-MS measurements. For R = iBu1H,13C and29Si NMR experiments confirmed the exclusive formation of 1a. Subsequent reactions of 1a with CuNHCDippCl and Au(PPh3)Cl result in formation of the neutral metal complex (CuNHCDipp)[Ge9{Si(iBu)3}3]·0.5 tol (2·0.5 tol) and the metal bridged dimeric unit {Au[Ge9{Si(iBu)3}3]2}–(3a), isolated as a (K-18c6)+salt in (K-18c6)Au[Ge9{Si(iBu)3}3]2·tol (3·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18-crown-6, crystals of the compound (K-18c6)2[Ge9{Si(iBu)3}2]·tol (4·tol), containing the bis-silylated cluster anion [Ge9(Si(iBu)3)2]2–(4a), were obtained. The compounds 2·0.5 tol, 3·tol and 4·tol were characterized by single-crystal structure determination.",

keywords = "Coinage Metals, Functionalization, Germanium, Silanes, Zintl clusters",

author = "Schiegerl, {Lorenz J.} and Geitner, {Felix S.} and Christina Fischer and Wilhelm Klein and F{\"a}ssler, {Thomas F.}",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = dec,

doi = "10.1002/zaac.201600295",

language = "English",

volume = "642",

pages = "1419--1426",

journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley-VCH Verlag",

number = "24",

}

Schiegerl, LJ, Geitner, FS, Fischer, C, Klein, W & Fässler, TF 2016, 'Functionalization of [Ge₉] with Small Silanes:[Ge₉(SiR₃)₃]^–(R = iBu, iPr, Et) and the Structures of (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃], (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂, and (K-18c6)₂[Ge₉{Si(iBu)₃}₂]', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 642, no. 24, pp. 1419-1426. https://doi.org/10.1002/zaac.201600295

Functionalization of [Ge₉] with Small Silanes:[Ge₉(SiR₃)₃]^–(R = iBu, iPr, Et) and the Structures of (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃], (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂, and (K-18c6)₂[Ge₉{Si(iBu)₃}₂]. / Schiegerl, Lorenz J.; Geitner, Felix S.; Fischer, Christina et al.
In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 642, No. 24, 12.2016, p. 1419-1426.

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

TY - JOUR

T1 - Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]–(R = iBu, iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K-18c6)Au[Ge9{Si(iBu)3}3]2, and (K-18c6)2[Ge9{Si(iBu)3}2]

AU - Schiegerl, Lorenz J.

AU - Geitner, Felix S.

AU - Fischer, Christina

AU - Klein, Wilhelm

AU - Fässler, Thomas F.

PY - 2016/12

Y1 - 2016/12

N2 - Novel silylation reactions at [Ge9] Zintl clusters starting from the chlorosilanes SiR3Cl (R = iBu, iPr, Et) and the Zintl phase K4Ge9are reported. The formation of the tris-silylated anions [Ge9(SiR3)3]–[R = iBu (1a), iPr (1b), Et (1c)] by heterogeneous reactions in acetonitrile was monitored by ESI-MS measurements. For R = iBu1H,13C and29Si NMR experiments confirmed the exclusive formation of 1a. Subsequent reactions of 1a with CuNHCDippCl and Au(PPh3)Cl result in formation of the neutral metal complex (CuNHCDipp)[Ge9{Si(iBu)3}3]·0.5 tol (2·0.5 tol) and the metal bridged dimeric unit {Au[Ge9{Si(iBu)3}3]2}–(3a), isolated as a (K-18c6)+salt in (K-18c6)Au[Ge9{Si(iBu)3}3]2·tol (3·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18-crown-6, crystals of the compound (K-18c6)2[Ge9{Si(iBu)3}2]·tol (4·tol), containing the bis-silylated cluster anion [Ge9(Si(iBu)3)2]2–(4a), were obtained. The compounds 2·0.5 tol, 3·tol and 4·tol were characterized by single-crystal structure determination.

AB - Novel silylation reactions at [Ge9] Zintl clusters starting from the chlorosilanes SiR3Cl (R = iBu, iPr, Et) and the Zintl phase K4Ge9are reported. The formation of the tris-silylated anions [Ge9(SiR3)3]–[R = iBu (1a), iPr (1b), Et (1c)] by heterogeneous reactions in acetonitrile was monitored by ESI-MS measurements. For R = iBu1H,13C and29Si NMR experiments confirmed the exclusive formation of 1a. Subsequent reactions of 1a with CuNHCDippCl and Au(PPh3)Cl result in formation of the neutral metal complex (CuNHCDipp)[Ge9{Si(iBu)3}3]·0.5 tol (2·0.5 tol) and the metal bridged dimeric unit {Au[Ge9{Si(iBu)3}3]2}–(3a), isolated as a (K-18c6)+salt in (K-18c6)Au[Ge9{Si(iBu)3}3]2·tol (3·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18-crown-6, crystals of the compound (K-18c6)2[Ge9{Si(iBu)3}2]·tol (4·tol), containing the bis-silylated cluster anion [Ge9(Si(iBu)3)2]2–(4a), were obtained. The compounds 2·0.5 tol, 3·tol and 4·tol were characterized by single-crystal structure determination.

KW - Coinage Metals

KW - Functionalization

KW - Germanium

KW - Silanes

KW - Zintl clusters

UR - http://www.scopus.com/inward/record.url?scp=85003013283&partnerID=8YFLogxK

U2 - 10.1002/zaac.201600295

DO - 10.1002/zaac.201600295

M3 - Article

AN - SCOPUS:85003013283

SN - 0044-2313

VL - 642

SP - 1419

EP - 1426

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

IS - 24

ER -

Functionalization of [Ge₉] with Small Silanes:[Ge₉(SiR₃)₃]^–(R = iBu, iPr, Et) and the Structures of (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃], (K-18c6)Au[Ge₉{Si(iBu)₃}₃]₂, and (K-18c6)₂[Ge₉{Si(iBu)₃}₂]

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