Heterobimetallic (Imido)antimony/Lithium Cages Containing [Sb(NR)(3)](3-) Trianions.
The reactions of [Sb(NMe(2))(3)] with the primary (amido)lithiums [PhCH(2)CH(2)N(H)Li](n)(), [CyN(H)Li](n)() (Cy = C(6)H(11)), [2,4-dmpN(H)Li](n)() [2,4-dmp = 2,4-(MeO)(2)C(6)H(3)], and [(t)()BuN(H)HLi](n)() give the heterobimetallic cage complexes [{Sb(NCH(2)CH(2)Ph)(3)}(2)Li(6).2THF] (1), [{Sb(NCy)(3)}(2)Li(6).2HNMe(2)].2C(6)H(5)CH(3) (2), [Sb{N(2,4-dmp)}(3)](2)Li(6).2THF.2C(6)H(5)CH(3) (3), and [{Sb(NBu(t)())(3)}(2)Li(6)] (4), respectively. The low-temperature X-ray structures of 1-4 show that they are composed of 14-membered polyhedral cages constructed from the association of two [Sb(NR)(3)](3)(-) trianions with six Li(+) cations. Crystal data; 2, triclinic, P&onemacr;, a = 12.775(6) Å, b = 13.191(9) Å, c = 11.015(5) Å, alpha = 111.55(4) degrees, beta = 95.39(4) degrees, gamma = 115.26(4) degrees; 3, triclinic P&onemacr;, a = 10.435(4) Å, b = 12.654(5) Å, c = 14.278(6) Å, alpha = 75.31(4) degrees, beta = 79.33(4) degrees, gamma = 84.33(4) degrees; 4, monoclinic P2(1)/c, a = 9.994(1) Å, b = 17.421(2) Å, c = 10.680(2) Å, beta = 111.33(1) degrees (the structure of 1 being reported previously). Lewis base solvation of the N(6)Li(6) substructures of 1-3 results in distortion and deformation of the Li frameworks. The structural variations in the cores of 1-4 indicate that the bonding in these species is dominated by the valence and bonding demands of the p block metal centers.
Beswick
Michael A.
MA
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K., and School of Applied Chemistry, University of North London, Holloway Road, London N7 8DB, U.K.
Choi
Nick
N
Harmer
Christopher N.
CN
Hopkins
Alexander D.
AD
McPartlin
Mary
M
Paver
Michael A.
MA
Raithby
Paul R.
PR
Steiner
Alexander
A
Tombul
Mustafa
M
Wright
Dominic S.
DS