Double Deprotonation of CH3CN by an Iron‐Aluminium Complex. Issue 16 (9th March 2023)

• Record Type: Journal Article
• Authors: Stadler, Benedek; Gorgas, Nikolaus; White, Andrew J. P.; Crimmin, Mark R.
• Is Part Of: Angewandte Chemie international edition. Volume 62:Issue 16(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-09
• Subjects: Aluminium -- C−H Activation -- Dianions -- Iron -- Nitriles; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202219212
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Herein we present the first double deprotonation of acetonitrile (CH3 CN) using two equivalents of a bimetallic iron‐aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] 2− dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH2 CN] − complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. [1, 2] The isolation of a [CHCN] 2− dianion through simple deprotonation of CH3 CN also offers the possibility of establishing a broader chemistry of this motif. Abstract : The double deprotonation of CH3 CN was achieved using an iron‐aluminium complex, yielding products containing a simple yet rare [HC=C=N] 2− dianion, characterised by X‐ray crystallography. DFT calculations suggest that the mechanism proceeds via a stepwise double deprotonation of the substrate by two equivalents of the bimetallic complex, with the intermediacy of a [NCCH2 ] − anion, which was observed spectroscopically in situ.