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

Angew Chem Int Ed Engl. 2016 Sep 12;55(38):11619-24. doi: 10.1002/anie.201605636. Epub 2016 Aug 9.

Authors

Tatsumi Ochiai¹, Tibor Szilvási², Daniel Franz³, Elisabeth Irran¹, Shigeyoshi Inoue^{4

5}

Affiliations

¹ Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
² Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, 1111, Budapest, Hungary.
³ Department of Chemistry, Catalysis Research Center and Institute of Silicon Chemistry, Technische Universität München, Lichtenbergstraße 4, 85748, Garching, Germany.
⁴ Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany. s.inoue@tum.de.
⁵ Department of Chemistry, Catalysis Research Center and Institute of Silicon Chemistry, Technische Universität München, Lichtenbergstraße 4, 85748, Garching, Germany. s.inoue@tum.de.

PMID: 27505126
DOI: 10.1002/anie.201605636

Abstract

The ditopic germanium complex FGe(NIPr)2 Ge[BF4 ] (3[BF4 ]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me3 Si)2 NGeNIPr (1) with BF3 ⋅OEt2 . This monocation is converted into the germylene-germyliumylidene 3[BAr(F) 4 ] [Ar(F) =3,5-(CF3 )2 -C6 H3 ] by treatment with Na[BAr(F) 4 ]. The tetrafluoroborate salt 3[BF4 ] reacts with 2 equivalents of Me3 SiOTf to give the novel complex (OTf)(GeNIPr)2 [OTf] (4[OTf]), which affords 4[BAr(F) 4 ] and 4[Al(OR(F) )4 ] [R(F) =C(CF3 )3 ] after anion exchange with Na[BAr(F) 4 ] or Ag[Al(OR(F) )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.

Publication types

Research Support, Non-U.S. Gov't