The reactions between t-BuP(O)(OH)(2) and equimolar quantities of MGaM
e4(M = Na, K) yield ionic and alkali metal containing molecular gallop
hosphonates [Na-4(mu(2)-OH2)(2)(THF)(2)][(Me2GaO3PBu-t)(2)](2) . 2THF(
2) and [K(THF)(6)][K-5(THF)(2){(Me2GaO3PBu-t)(2)}(3)] (3), respectivel
y. Compounds 2 and 3 are soluble in common organic solvents and have b
een characterized by means of analytical and spectroscopic techniques,
as well as by single-crystal X-ray diffraction studies. These compoun
ds represent the rare examples of molecular ionic phosphonate cages wh
ich contain coordinated Na+ or K+ ions. Compound 2 is constructed from
-two eight-membered Ga2O4P2 gallium phosphonate rings which sandwich a
central Na-4(H2O)(2) unit. In the case of 3, three eight-membered Ga2
O4P2 gallium phosphonate units envelope an aggregated K-5 core which e
xists in the form of a trigonal bipyramidal polyhedron. The Na+ and K ions in 2 and 3 are also coordinated by the endocyclic oxygen atoms o
f the eight-membered gallophosphonate crowns, apart from the regular e
xocyclic P-O coordination. Unlike the lithium gallophosphonate [Li-4(T
HF)(4)][{(MeGaO3PBu-t)(3)(mu(3)-O-2)}(2)] (1), compounds 2 and 5 do no
t undergo any clean cage conversion reaction in the, presence of 15-cr
own-5 and 18-crown-6, respectively.