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
datasetposted on 03.03.2017 by Jana Weßing, Christoph Göbel, Birgit Weber, Christian Gemel, Roland A. Fischer
Datasets usually provide raw data for analysis. This raw data often comes in spreadsheet form, but can be any collection of data, on which analysis can be performed.
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).