Abstract
Reactions of the coinage metal (CM) cyanides, CuCN, AgCN, or K[Au(CN)2], with [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3) result in KCN metathesis and a series of “alumina-Gilman” reagents, [({SiNDipp}Al)2CM]K (CM = Cu, Ag, or Au). The latter species may be isolated in both charge-separated, [({SiNDipp}Al)2CM]−[K(THF)6]+, or contact ion pair forms when crystallized in the presence or absence of THF. Computational analysis apportions a high degree of covalency to the CM–Al metal bonding and attribution of an aluminum oxidation state that is best represented as Al(II). This latter inference is supported by the experimental observation of THF activation, deduced to result from the competitive single electron reduction of the group 11 center during the synthesis of the bis(alumanyl)metalates. UV photolysis of [({SiNDipp}Al)2Ag]K provided a product of 2-fold Al(II) radical addition to benzene. This species is also synthesized by a modification of the reaction that gave rise to the initially identified cuprate metathesis product. The intermediacy of [{SiNDipp}Al•] radicals, which are proposed to add to benzene in a stepwise manner, is supported by the observation of in situ recorded EPR spectra, the simulated parameters of which have been assigned to the singly aluminated benzene product, [{SiNDipp}Al(C6H6)•].
Original language | English |
---|---|
Pages (from-to) | 3074-3086 |
Number of pages | 13 |
Journal | Organometallics |
Volume | 43 |
Issue number | 23 |
Early online date | 26 Nov 2024 |
DOIs | |
Publication status | Published - 9 Dec 2024 |
Data Availability Statement
This research made use of the Anatra High Throughput Computing (HTC) Cluster at the University of Bath.Acknowledgements
The authors gratefully acknowledge the University of Bath\u2019s Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work. We also thank Prof. Ching-Wen Chiu and Yu-Jiang Lin for helpful conversations.Funding
The authors gratefully acknowledge the Leverhulme Trust Project Award (RPG-2023-104) \u201CAlkaline Element Z-type Ligands for Tunable Base Metal Catalysis\u201D.
Funders | Funder number |
---|---|
Leverhulme Trust | RPG-2023-104 |