The Diverse Reactivity of an Al(I) Carbenoid Towards Phosphorus‐Based Ylides. The Crucial Role of Co‐Crystallised Lithium Halide
Attempts to generate NacNacAl-based (NacNac=[ArNC(Me)CHC(Me)NAr]<sup>-</sup>; Ar=2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) alkylidenes via reactions with trimethyl(methylidene), triphenyl(methylidene) and triethyl(ethylidene) phosphiranes led to new and unexpected reactivity patterns. Reaction with Me<sub>3</sub>P=CH<sub>2</sub> resulted in the intermolecular deprotonation of the NacNac -CCH<sub>3</sub> backbone. Reaction with Ph<sub>3</sub>P=CH<sub>2</sub>*LiI afforded an equimolar mixture of NacNacAlH<sub>2</sub> and the ortho-metalated adduct, NacNac'Al(η(C,C)<sup>2</sup>-CH<sub>2</sub>=PPh<sub>2</sub>(o-C<sub>6</sub>H<sub>4</sub>)) (NacNac'=[ArNC(Me)CHC(=CH<sub>2</sub>)NAr]<sup>2-</sup>). Finally, the use of Et<sub>3</sub>P=CHMe*LiBr resulted in the fragmentation of the NacNac moiety.
Authors
- Georgii I. Nikonov (ORCID: https://orcid.org/0000-0001-6489-4160)
- Anton Dmitrienko
- Melanie Pilkington
Institutions
- Brock University (CA)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-02-05
- DOI
- https://doi.org/10.1002/chem.202500273
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Brock University
- Natural Sciences and Engineering Research Council of Canada