Isolation and Structure of Germylene-Germyliumylidenes Stabilized by N-Heterocyclic Imines

Tatsumi Ochiai; Tibor Szilvási; Daniel Franz; Elisabeth Irran; Shigeyoshi Inoue

doi:10.1002/anie.201605636

Isolation and Structure of Germylene-Germyliumylidenes Stabilized by N-Heterocyclic Imines

Tatsumi Ochiai
, Tibor Szilvási
, Daniel Franz
, Elisabeth Irran
, Shigeyoshi Inoue

Chair of Silicon Chemistry

Technische Universität Berlin
Technical University of Budapest
Technical University of Munich

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

60 Scopus citations

Abstract

The ditopic germanium complex FGe(NIPr)₂Ge[BF₄] (3[BF₄]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me₃Si)₂NGeNIPr (1) with BF₃⋅OEt₂. This monocation is converted into the germylene-germyliumylidene 3[BAr^F₄] [Ar^F=3,5-(CF₃)₂-C₆H₃] by treatment with Na[BAr^F₄]. The tetrafluoroborate salt 3[BF₄] reacts with 2 equivalents of Me₃SiOTf to give the novel complex (OTf)(GeNIPr)₂[OTf] (4[OTf]), which affords 4[BAr^F₄] and 4[Al(OR^F)₄] [R^F=C(CF₃)₃] after anion exchange with Na[BAr^F₄] or Ag[Al(OR^F)₄], respectively. The computational, as well as crystallographic study, reveals that 4⁺has significant bis(germyliumylidene) dication character.

Original language	English
Pages (from-to)	11619-11624
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	38
DOIs	https://doi.org/10.1002/anie.201605636
State	Published - 12 Sep 2016

Keywords

cations
density-functional calculations
germanium
solid-state structures
structure elucidation

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10.1002/anie.201605636

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title = "Isolation and Structure of Germylene-Germyliumylidenes Stabilized by N-Heterocyclic Imines",

abstract = "The ditopic germanium complex FGe(NIPr)2Ge[BF4] (3[BF4]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me3Si)2NGeNIPr (1) with BF3⋅OEt2. This monocation is converted into the germylene-germyliumylidene 3[BArF4] [ArF=3,5-(CF3)2-C6H3] by treatment with Na[BArF4]. The tetrafluoroborate salt 3[BF4] reacts with 2 equivalents of Me3SiOTf to give the novel complex (OTf)(GeNIPr)2[OTf] (4[OTf]), which affords 4[BArF4] and 4[Al(ORF)4] [RF=C(CF3)3] after anion exchange with Na[BArF4] or Ag[Al(ORF)4], respectively. The computational, as well as crystallographic study, reveals that 4+has significant bis(germyliumylidene) dication character.",

keywords = "cations, density-functional calculations, germanium, solid-state structures, structure elucidation",

author = "Tatsumi Ochiai and Tibor Szilv{\'a}si and Daniel Franz and Elisabeth Irran and Shigeyoshi Inoue",

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

year = "2016",

month = sep,

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doi = "10.1002/anie.201605636",

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T1 - Isolation and Structure of Germylene-Germyliumylidenes Stabilized by N-Heterocyclic Imines

AU - Ochiai, Tatsumi

AU - Szilvási, Tibor

AU - Franz, Daniel

AU - Irran, Elisabeth

AU - Inoue, Shigeyoshi

PY - 2016/9/12

Y1 - 2016/9/12

N2 - The ditopic germanium complex FGe(NIPr)2Ge[BF4] (3[BF4]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me3Si)2NGeNIPr (1) with BF3⋅OEt2. This monocation is converted into the germylene-germyliumylidene 3[BArF4] [ArF=3,5-(CF3)2-C6H3] by treatment with Na[BArF4]. The tetrafluoroborate salt 3[BF4] reacts with 2 equivalents of Me3SiOTf to give the novel complex (OTf)(GeNIPr)2[OTf] (4[OTf]), which affords 4[BArF4] and 4[Al(ORF)4] [RF=C(CF3)3] after anion exchange with Na[BArF4] or Ag[Al(ORF)4], respectively. The computational, as well as crystallographic study, reveals that 4+has significant bis(germyliumylidene) dication character.

AB - The ditopic germanium complex FGe(NIPr)2Ge[BF4] (3[BF4]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me3Si)2NGeNIPr (1) with BF3⋅OEt2. This monocation is converted into the germylene-germyliumylidene 3[BArF4] [ArF=3,5-(CF3)2-C6H3] by treatment with Na[BArF4]. The tetrafluoroborate salt 3[BF4] reacts with 2 equivalents of Me3SiOTf to give the novel complex (OTf)(GeNIPr)2[OTf] (4[OTf]), which affords 4[BArF4] and 4[Al(ORF)4] [RF=C(CF3)3] after anion exchange with Na[BArF4] or Ag[Al(ORF)4], respectively. The computational, as well as crystallographic study, reveals that 4+has significant bis(germyliumylidene) dication character.

KW - cations

KW - density-functional calculations

KW - germanium

KW - solid-state structures

KW - structure elucidation

UR - https://www.scopus.com/pages/publications/84991696145

U2 - 10.1002/anie.201605636

DO - 10.1002/anie.201605636

M3 - Article

AN - SCOPUS:84991696145

SN - 1433-7851

VL - 55

SP - 11619

EP - 11624

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 38

ER -

Isolation and Structure of Germylene-Germyliumylidenes Stabilized by N-Heterocyclic Imines

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