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