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.
Inorg Chem
; 56(6): 3517-3525, 2017 Mar 20.
Article
em En
| MEDLINE
| ID: mdl-28257180
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 11 and 12 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).
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2017
Tipo de documento:
Article
País de afiliação:
Alemanha
País de publicação:
EEUU
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ESTADOS UNIDOS
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ESTADOS UNIDOS DA AMERICA
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EUA
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UNITED STATES
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UNITED STATES OF AMERICA
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US
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USA