AI Article Synopsis
- - The reaction of MeAlCl2 with PhPLi2 in THF produces a complex that has a unique cubic structure similar to zeolites, with significant voids, for the aluminum case and its gallium and indium counterparts formed in situ from similar reactions.
- - The resulting complexes [{MeAl(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+ (1) for aluminum, along with the gallium (2) and indium (3) analogues show variations in the behavior and environment of lithium (Li+) counterions due to differences in packing and lattice energy.
- - Comprehensive analysis via X-ray crystallography, solid-state NMR, and DFT
Article Abstract
The reaction of MeAlCl2 with 'PhPLi2' in THF gives [{MeAl(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+ (1). The GaIII and InIII analogues, [{MeE(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+(THF)3 (E=Ga (2), In (3)), are obtained by the in situ reactions of MeECl2 with PhPLi2 in THF. For all of the complexes, the cage anions have an unusual cubic arrangement that is similar to a zeolite, and contain large voids (ca. 17 A). The location of the Li+ counterions in 1-3 and their coordination environment appears to subtly reflect variations in packing and lattice energy. Whereas in 1 highly mobile, loosely coordinated Li+ counterions are present, 2 and 3 contain less mobile THF-solvated counterions within the cavities. X-ray crystallographic and solid-state NMR studies are reported on 1-3, together with model DFT calculations on the selectivity of halide coordination.
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| http://dx.doi.org/10.1002/chem.200600781 | DOI Listing |
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