Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] and K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]

Felix S. Geitner; Wilhelm Klein; Oksana Storcheva; T. Don Tilley; Thomas F. Fässler

doi:10.1021/acs.inorgchem.9b02158

Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp₂(MeCN)Ti(ν¹-Ge₉{Si(TMS)₃}₃)] and K₃[Cp₂Ti(ν¹-Ge₉{Si(TMS)₃}₂)₂]

Felix S. Geitner, Wilhelm Klein, Oksana Storcheva, T. Don Tilley, Thomas F. Fässler

Chair of Inorganic Chemistry with Focus on New Materials

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

15 Scopus citations

Abstract

Anionic clusters with a homoatomic [Ge₉] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge₉] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp₂(MeCN)Ti(ν¹-Ge₉{Si(TMS)₃}₃)] (1) was obtained by the reaction of K[Ge₉{Si(TMS)₃}₃] with [Cp₂TiCl]₂ in toluene as dark orange crystals, whereas the reaction of K₂[Ge₉{Si(TMS)₃}₂] with [Cp₂TiCl]₂ in thf and subsequent recrystallization from toluene resulted in dark green crystals of K₃[Cp₂Ti(ν¹-Ge₉{Si(TMS)₃}₂)₂] (2). Compound 2 contains the trianion [Cp₂Ti(ν¹-Ge₉{Si(TMS)₃}₂)₂]^3- (2a), which can be described either as a [Cp₂Ti]⁺-bridged [Ge₉{Si(TMS)₃}₂]^2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge₉] clusters and Ti(III). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.

Original language	English
Pages (from-to)	13293-13298
Number of pages	6
Journal	Inorganic Chemistry
Volume	58
Issue number	19
DOIs	https://doi.org/10.1021/acs.inorgchem.9b02158
State	Published - 7 Oct 2019

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@article{939ca3cee20a403bb75698b6a1246e10,

title = "Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] and K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]",

abstract = "Anionic clusters with a homoatomic [Ge9] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge9] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] (1) was obtained by the reaction of K[Ge9{Si(TMS)3}3] with [Cp2TiCl]2 in toluene as dark orange crystals, whereas the reaction of K2[Ge9{Si(TMS)3}2] with [Cp2TiCl]2 in thf and subsequent recrystallization from toluene resulted in dark green crystals of K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2] (2). Compound 2 contains the trianion [Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]3- (2a), which can be described either as a [Cp2Ti]+-bridged [Ge9{Si(TMS)3}2]2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge9] clusters and Ti(III). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.",

author = "Geitner, {Felix S.} and Wilhelm Klein and Oksana Storcheva and Tilley, {T. Don} and F{\"a}ssler, {Thomas F.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = oct,

day = "7",

doi = "10.1021/acs.inorgchem.9b02158",

language = "English",

volume = "58",

pages = "13293--13298",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp₂(MeCN)Ti(ν¹-Ge₉{Si(TMS)₃}₃)] and K₃[Cp₂Ti(ν¹-Ge₉{Si(TMS)₃}₂)₂]. / Geitner, Felix S.; Klein, Wilhelm; Storcheva, Oksana et al.
In: Inorganic Chemistry, Vol. 58, No. 19, 07.10.2019, p. 13293-13298.

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

TY - JOUR

T1 - Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters

T2 - Synthesis and Characterization of [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] and K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]

AU - Geitner, Felix S.

AU - Klein, Wilhelm

AU - Storcheva, Oksana

AU - Tilley, T. Don

AU - Fässler, Thomas F.

PY - 2019/10/7

Y1 - 2019/10/7

N2 - Anionic clusters with a homoatomic [Ge9] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge9] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] (1) was obtained by the reaction of K[Ge9{Si(TMS)3}3] with [Cp2TiCl]2 in toluene as dark orange crystals, whereas the reaction of K2[Ge9{Si(TMS)3}2] with [Cp2TiCl]2 in thf and subsequent recrystallization from toluene resulted in dark green crystals of K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2] (2). Compound 2 contains the trianion [Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]3- (2a), which can be described either as a [Cp2Ti]+-bridged [Ge9{Si(TMS)3}2]2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge9] clusters and Ti(III). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.

AB - Anionic clusters with a homoatomic [Ge9] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge9] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp2(MeCN)Ti(ν1-Ge9{Si(TMS)3}3)] (1) was obtained by the reaction of K[Ge9{Si(TMS)3}3] with [Cp2TiCl]2 in toluene as dark orange crystals, whereas the reaction of K2[Ge9{Si(TMS)3}2] with [Cp2TiCl]2 in thf and subsequent recrystallization from toluene resulted in dark green crystals of K3[Cp2Ti(ν1-Ge9{Si(TMS)3}2)2] (2). Compound 2 contains the trianion [Cp2Ti(ν1-Ge9{Si(TMS)3}2)2]3- (2a), which can be described either as a [Cp2Ti]+-bridged [Ge9{Si(TMS)3}2]2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge9] clusters and Ti(III). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.

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U2 - 10.1021/acs.inorgchem.9b02158

DO - 10.1021/acs.inorgchem.9b02158

M3 - Article

C2 - 31532208

AN - SCOPUS:85072916354

SN - 0020-1669

VL - 58

SP - 13293

EP - 13298

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -

Early-Transition-Metal Complexes of Functionalized Nonagermanide Clusters: Synthesis and Characterization of [Cp₂(MeCN)Ti(ν¹-Ge₉{Si(TMS)₃}₃)] and K₃[Cp₂Ti(ν¹-Ge₉{Si(TMS)₃}₂)₂]

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