1,4-dioxobenzene compounds of gallium: reversible binding of pyridines to [[((t)Bu)(2)Ga](2)(mu-OC(6)H(4)O)](n) in the solid state.

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The gallium aryloxide polymer, [[((t)Bu)(2)Ga](2)(mu-OC(6)H(4)O)](n)(1) is synthesized by the addition of Ga((t)()Bu)(3) with hydroquinone in a noncoordinating solvent, and reacts with pyridines to yield the yellow compound [((t)()Bu)(2)Ga(L)](2)(mu-OC(6)H(4)O) [L = py (2), 4-Mepy (3), and 3,5-Me(2)py (4)] via cleavage of the Ga(2)O(2) dimeric core. The analogous formation of Ga((t)()Bu)(2)(OPh)(py) (5) occurs by dissolution of [((t)Bu)(2)Ga(mu-OPh)](2) in pyridine. In solution, 2-4 undergo dissociation of one of the pyridine ligands to yield [((t)()Bu)(2)Ga(L)(mu-OC(6)H(4)O)Ga((t)Bu)(2)](2), for which the DeltaH and DeltaS have been determined. Thermolysis of compounds 2-4 in the solid-state results in the loss of the Lewis base and the formation of 1. The reaction of 1 or [((t)Bu)(2)Ga(mu-OPh)](2) with the vapor of the appropriate ligand results in the solid state formation of 2-4 or 5, respectively. The deltaH and deltaS for both ligand dissociation and association for the solid-vapor reactions have been determined. The interconversion of 1 into 2-4, as well as [((t)Bu)(2)Ga(mu-OPh)](2) into 5, and their reverse reactions, have been followed by (13)C CPMAS NMR spectroscopy, TG/DTA, SEM, EDX, and powder XRD. Insight into this solid-state polycondensation polymerization reaction may be gained from the single-crystal X-ray crystallographic packing diagrams of 2-5. The crystal packing for compounds 2, 3, and 5 involve a head-to-head arrangement that is maintained through repeated ligand dissociation and association cycles. In contrast, when compound 4 is crystallized from solution a head-to-tail packing arrangement is formed, but during reintroduction of 3,5-Me(2)py in the solid state-vapor reaction of compound 1, a head-to-head polymorph is postulated to account for the alteration in the deltaH of subsequent ligand dissociation reactions. Thus, the deltaH for the condensation polymerization reaction is dependent on the crystal packing; however, the subsequent reversibility of the reaction is dependent on the polymorph.