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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

Title data

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. Vol. 56 (2017) Issue 6 . - pp. 3517-3525.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.6b03127

Abstract in another language

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).

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV > Chair Anorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 25 Jul 2017 11:26
Last Modified: 25 Jul 2017 11:26
URI: https://eref.uni-bayreuth.de/id/eprint/38800