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Title: Di-tert-butyl phosphate as synthon for metal phosphate materials via single-source coordination polymers [M(dtbP)(2)](n) (M = Mn, Cu) and [Cd(dtbP)(2)(H(2)O)](n) (dtbp-H = (tBuO)(2)P(O)OH)
Keywords: Di(Tert-Butyl)Phosphate Complexes
Tris(Tert-Butoxy)Siloxy Complexes
Zincophosphate Structures
Aluminum Phosphate
Diethyl Phosphate
Issue Date: 2002
Citation: INORGANIC CHEMISTRY, 41(24), 6404-6411
Abstract: Reaction of M(OAc)(2).xH(2)O (M = Mn, Cu, or Cd) with di-tert-butyl phosphate (dtbp-H) in a 1:2 molar ratio in methanol followed by slow crystallization of the resultant solid in MeOH/THF medium results in the formation of three new polymeric metal phosphates [M(dtbP)(2)](n) [M = Mn, 1 (beige); M = Cu, 2 (blue)] and [Cd(dtbP)(2)(H(2)O)](n), 3 (colorless)] in good yields. The formation of [Mn(dtbP)21, (1) proceeds via tetrameric manganese phosphate [Mn(4)(O)(dtbP)(6)] (4), which has been isolated in an analytically pure form. Perfectly air- and moisture-stable compounds 1-4 were characterized with the aid of analytical, thermoanalytical, and spectroscopic techniques. The molecular structures of 1-3 were further established by single-crystal X-ray diffraction studies. Crystal data for 1: C(32)H(72)-Mn(2)O(16)P(4), monoclinic, P2(1)/c, a = 19.957(4) Angstrom, b = 13.419(1) Angstrom, c = 18.083(2) Angstrom, beta = 91.25(2)degrees, Z = 4. Crystal data for 2: C(16)H(36)CUO(8)P(2), orthorhombic, Pccn, a = 23.777(2) Angstrom, b = 10.074(1) Angstrom, c = 10.090(1) Angstrom, Z = 4. Crystal data for 3: C(48)H(114)Cd(3)O(27)P(6), triclinic, P (1) over bar, a = 12.689(3) Angstrom, b = 14.364(3) Angstrom, c = 22,491(5) Angstrom, alpha = 84.54(3)degrees, beta = 79.43(3)degrees, gamma = 70.03(3)degrees, Z = 2. The diffraction studies reveal three different structural forms for the three compounds investigated, each possessing a one-dimensional coordination polymeric structure. While alternating triple and single dtbp bridges are found between the adjacent Mn(2+) ions in 1, uniform double dtbp bridges across the adjacent Cu(2+) ions are present in 2. The cadmium ions in the structure of 3 are pentacoordinated. Thermal analysis (TGA and DSC) indicates that compounds 1-3 convert to the corresponding crystalline metaphosphate materials M(PO(3))(2), in each case at temperatures below 500 degreesC. Similarly, the thermal decomposition of 4 results in the formation of Mn(PO(3))(3) and Mn(2)P(2)O(7). The final materials obtained by independent thermal decomposition of bulk samples have been characterized using I R spectroscopic, powder diffraction, and N(2) adsorption studies.
ISSN: 0020-1669
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