Structural, solid-state NMR and theoretical studies of the inverse-coordination of lithium chloride using group 13 phosphide hosts.
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.
Duer
Melinda J
MJ
Chemistry Department, Cambridge University, Lensfield Road, Cambridge CB2 1EW, UK.
García
Felipe
F
Goodman
Jonathan M
JM
Hehn
Jörg P
JP
Kowenicki
Richard A
RA
Naseri
Vesal
V
McPartlin
Mary
M
Stead
Matthew L
ML
Stein
Robin
R
Wright
Dominic S
DS