Abstract
The potassium aluminyl K[Al(NON)] ([NON] 2−=[O(SiMe 2NDipp) 2] 2−, Dipp=2,6-iPr 2C 6H 3) reacts with group 14 chloroamidinates E {14}(Am)Cl (E {14}=Ge, Sn, Pb. [Am] −=[tBuC(NDipp) 2] −) to form (NON)Al−E {14}(Am) Lewis pairs with unsupported Al−E {14} bonds, including the first structurally authenticated Al−Pb bond. Analysis using spectroscopic (NMR, UV-vis and Mössbauer for E {14}=Sn), X-ray diffraction and computational (DFT, QTAIM, TD-DFT) methods conclude an Al−E {14} σ-bond derived from a Lewis basic Al and a Lewis acidic tetrylene, with back-donation from the E {14} s-orbital lone pair donor NBO to acceptor NBOs on Al that are derived from s/p-orbitals. The reaction of the Al−Ge compound with CO 2 forms the dioxocarbene (NON)Al(μ-O 2C)Ge(Am), whilst under the same conditions the Al−Sn compound reacts with additional CO 2 to form the carbonate, (NON)Al(μ-CO 3)Sn(Am). Addition of ethene to the Al−E {14} (E {14}=Ge, Sn) compounds introduces an ethylene bridge between the aluminium and group 14 atoms forming a frustrated Lewis pair (FLP). Reaction of the (Al/Ge) FLP with CO 2 forms an activation product with new Al−O and Ge−C bonds, whilst reaction with iPrN=C=NiPr proceeds with insertion into the Al−C bond to form an aluminium amidinate.
Original language | English |
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Article number | e202404206 |
Journal | Chemistry - A European Journal |
Volume | 31 |
Issue number | 7 |
Early online date | 4 Dec 2024 |
DOIs | |
Publication status | Published - 3 Feb 2025 |
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.Acknowledgements
We acknowledge experiments by Dr Simon Granville and Prof Nick Cox who examined compound 1 c using SQUID magnetometry and EPR spectroscopy, respectively, concluding that there is no appreciable radical character. The authors gratefully acknowledge the University of Bath’s Research Computing Group (http://doi.org/10.15125/b6cd-s854) for their support in this workKeywords
- CO activation
- aluminyl
- frustrated Lewis pair (FLP)
- heterobimetallic
- tetrylene
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Organic Chemistry
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