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- Title
Normal-to-Abnormal NHC Rearrangement of Al<sup>III</sup>, Ga<sup>III</sup>, and In<sup>III</sup> Trialkyl Complexes: Scope, Mechanism, Reactivity Studies, and H<sub>2</sub> Activation.
- Authors
Schnee, Gilles; Nieto Faza, Olalla; Specklin, David; Jacques, Béatrice; Karmazin, Lydia; Welter, Richard; Silva López, Carlos; Dagorne, Samuel
- Abstract
The present contribution reports experimental and theoretical mechanistic investigations on a normal-to-abnormal (C2-to-C4-bonded) NHC rearrangement processes occurring with bulky group 13 metal NHC adducts, including the scope of such a reactivity for Al compounds. The sterically congested adducts ( nI tBu)MMe3 ( nI tBu=1,3-di- tert-butylimidazol-2-ylidene; M=Al, Ga, In; 1 a- c) readily rearrange to quantitatively afford the corresponding C4-bonded complexes ( aI tBu)MMe3 ( 4 a- c), a reaction that may be promoted by THF. Thorough experimental data and DFT calculations were performed on the nNHC-to- aNHC process converting the Al- nNHC ( 1 a) to its aNHC analogue 4 a. A nI tBu/ aI tBu isomerization is proposed to account for the formation of the thermodynamic product 4 a through reaction of transient aI tBu with THF-AlMe3. The reaction of benzophenone with ( nI tBu)AlMe3 afforded the zwitterionic species ( aI tBu)(CPh2-O-AlMe3) ( 6), reflecting the unusual reactivity that such bulky adducts may display. Interestingly, the nI tBu/Al( iBu)3 Lewis pair behaves like a frustrated Lewis pair (FLP) since it readily reacts with H2 under mild conditions. This may open the way to future reactivity developments involving commonly used trialkylaluminum precursors.
- Subjects
REARRANGEMENTS (Chemistry); ALUMINUM compounds; THERMODYNAMICS research; ISOMERIZATION; BENZOPHENONES
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 49, p17959
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201503000