| The synthesis and characterization of a novel class of covalent early transition metal aryloxide network compounds has been performed. The reaction of M(OR)4 (M = titanium, vanadium, R = iPr; or zirconium, R = Et) with a dihydroxy functionalized organic spacer (hydroquinone, resorcinol, 4,4′-biphenol, 2,6- or 2,7-dihydroxynaphthalene) in various solvents (diethyl ether, tetrahydrofuran, carbon disulfide or 4-R-pyridine (R = H, CH3, or phenylpropyl)) at 100°C often affords microcrystalline material. The compounds have been characterized by powder X-ray diffraction and, when crystal size permitted, single crystal diffraction techniques using both conventional and synchrotron X-ray sources.;When strong donor solvents are employed, the one-dimensional chains [O=V(μ 2,6-OC10H6O)(4-(3-Ph-propyl)py)2] n (11), [O=V(μ1,4-OC6H4O)(py) 2]n (12) and [cis-Ti(μ 2,7-OC10H6O)2(py)2] n (14) or two-dimensional sheets [cis-Zr(μ 1,4-OC6H4O)2(py)2] n (6-Zr), [trans-M(μ1,4-OC 6H4O)2(py)2·(py)]n (7, M=Ti, V), [trans-M(μ1,4-OC 6H4O)2(4-Ph-py)2]n ( 8, M=Ti,V), [trans-Ti(μ1,3-OC6 H4O)2(py)2]n (9), [trans-Ti(μ1,3-OC6H4O) 2(4-Ph-py)2]n (10), [mer -V(μ2,6-OC10H6O)1.5(4-(3-(Ph-propyl)py) 3]n (13) and [cis-Ti(μ 2,7-OC10H6O)2(4-Me-py)2·(4-Me-py) 0.5]n (15) form. The use of TiCl4 as the metal starting material also results in lowered dimensionality. The one-dimensional chains {[cis-TiCl4(μ1,4 -OC6H4O)](pyH)2}n ( 16) and [trans-cis-cis-TiCl2(μ 2,6-OC10H6O)(THF)2]n ( 17) and the two-dimensional sheet {[TiCl(μ-4,4′-OC 12H8O)0.5(μ:η1,η 2-4,4′-OC12H8O)]2 ·THF}n (18) have been characterized.;In contrast, when less donating solvents are used, condensed three-dimensional nets based on a Ti2(μ-OR)2 core are formed. {[Ti(μ 1,6-4,4′-OC12H8O)0.5 (μ1,6:η2,η1-4,4 ′-OC12H8O)(OiPr)(HO iPr)]2·THF}n (1) is a six connected network exhibiting a base centered structure, {[Ti(μ2,7 -OC10H6O)(μ2,7:η2,η 1-OC10H6OH)(OiPr)]2} n (2) and {[Ti(μ2,6-OC10H 6O)0.5(μ2,6:η2,η 1-OC10H6O)(μ2,6-OC10H 6OH)]2·3C6H6}n ( 3) are both eight connected networks, exhibiting body centered and rhombic motifs, respectively. In addition, the bridging disposition of the spacer ligand can affect the dimensionality and topology of the network material obtained. The shorter reach of the 1,3-diphenoxide only allowed the two-dimensional sheet {[Ti(μ1,3-OC6H4O)(μ-1,3-OC 6H4OH)(1,3-OC6H4OH)(HOiPr)] 2}n (4) to form. |
