ABSTRACT
A non-solvated alkyl-substituted Al(I) anion dimer was synthesized by a reduction of haloalumane precursor using a mechanochemical method. The crystallographic and theoretical analysis revealed its structure and electronic properties. Experimental XPS analysis of the Al(I) anions with reference compounds revealed the lower Alâ 2p binding energy corresponds to the lower oxidation state of Al species. It should be emphasized that the experimentally obtained XPS binding energies were reproduced by delta SCF calculations and were linearly correlated with NPA charges and 2p orbital energies.
ABSTRACT
Base-stabilized neutral oxoborane and thioxoborane supported by a bis(oxazolinyl)(phenyl)methanide ligand have been synthesized and structurally characterized. While previous synthetic attempts of oxoborane ligated by ß-diketiminate (NacNac) did not allow for its isolation in acid-free form, oxoborane supported by a bis(oxazolinyl)(phenyl)methanide ligand is isolable, due to the absence of imine É-protons and steric protection of enamine carbon. Crystallographic analysis revealed the presence of a B-O double bond close to the shortest end of the reported lengths. Its reactivity has also been examined, and it was majorly governed by the nucleophilicity and basicity of the oxygen atom. The chemical inertness and synthetic convenience of the bis(oxazolinyl)(phenyl)methanide scaffold presented in this work suggest its utility as an innocent alternative to the NacNac scaffold.
