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Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe₃)₂)₂](TM = Fe, Co, Zn) : Insertion, Cp* Transfer, and Orthometalation

Titelangaben

Weßing, Jana ; Göbel, Christoph ; Weber, Birgit ; Gemel, Christian ; Fischer, Roland A.:
Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe₃)₂)₂](TM = Fe, Co, Zn) : Insertion, Cp* Transfer, and Orthometalation.
In: Inorganic Chemistry. Bd. 56 (2017) Heft 6 . - S. 3517-3525.
ISSN 1520-510X
DOI: 10.1021/acs.inorgchem.6b03127

Abstract

The reactivity of the carbenoid group 13 metal ligands ECp* (E = Al, Ga) toward low valent transition metal complexes [TM(btsa)2] (TM = Fe, Co, Zn; btsa = bis(trimethylsilyl)amide) was investigated, revealing entirely different reaction patterns for E = Al and Ga. Treatment of [Co(btsa)2] with AlCp* yields [Cp*Co(μ-H)(Al(κ2-(CH2SiMe2)NSiMe3)(btsa))] (1) featuring an unusual heterometallic bicyclic structure that results from the insertion of AlCp* into the TM–N bond with concomitant ligand rearrangement including C−H activation at one amide ligand. For [Fe(btsa)2], complete ligand exchange gives FeCp*2, irrespective of the employed stoichiometric ratio of the reactants. In contrast, treatment of [TM(btsa)2] (TM = Fe, Co) with GaCp* forms the 1:1 and 1:2 adducts [(GaCp*)Co(btsa)2] (2) and [(GaCp*)2Fe(btsa)2] (3), respectively. The tendency of AlCp* to undergo Cp* transfer to the TM center appears to be dependent on the nature of the TM center: For [Zn(btsa)2], no Cp* transfer is observed on reaction with AlCp*; instead, the insertion product [Zn(Al(η2-Cp*)(btsa))2] (4) is formed. In the reaction of [Co(btsa)2] with the trivalent [Cp*AlH2], transfer of the amide ligands without further ligand rearrangement is observed, leading to [Co(μ-H)4(Al(η2-Cp*)(btsa))2] (5).

Weitere Angaben

Publikationsform: Artikel in einer Zeitschrift
Begutachteter Beitrag: Ja
Institutionen der Universität: Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie II > Professur Anorganische Chemie II - Univ.-Prof. Dr. Birgit Weber
Fakultäten
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie II
Titel an der UBT entstanden: Nein
Themengebiete aus DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Eingestellt am: 25 Jul 2017 11:26
Letzte Änderung: 25 Jul 2017 11:26
URI: https://eref.uni-bayreuth.de/id/eprint/38800