The reaction of Fe(III) with Na(+) and K(+) salts of the trivacant [alpha-SiW(9)O(34)](10)(-) ligand have been investigated at pH 6 and pH 1. A new dimer, [(alpha-SiFe(3)W(9)(OH)(3)O(34))(2)(OH)(3)](11-) (1), is synthesized by reacting Na(7)H(3)[alpha-SiW(9)O(34)] or K(10)[alpha-SiW(9)O(34)] with exactly 3 equiv of Fe(III) in a 0.5 M sodium acetate solution (pH 6). The structure of 1, determined by single-crystal X-ray diffraction (a = 22.454(2) A, b = 12.387(2) A, c = 37.421(2), beta = 100.107(8) degrees , monoclinic, C2/c, Z = 4, R(1) = 5.11% based on 12739 independent reflections), consists of two [alpha-SiFe(3)W(9)(OH)(3)O(34)](4-) units linked by three Fe-mu-OH-Fe bonds. Reaction of K(10)[alpha-SiW(9)O(34)] with 3 equiv of Fe(III) in water (pH 1) yields [(alpha-Si(FeOH(2))(2)FeW(9)(OH)(3)O(34))(2)](8)(-2). The structure of 2 was also determined by single-crystal X-ray diffraction (a = 36.903(2) A, b = 13.9868(9) A, c = 21.7839(13) A, beta = 122.709(1) degrees , monoclinic, C2/c, Z = 4, R(1) = 4.57% based on 11787 independent reflections). It consists of two [alpha-Si(FeOH(2))(2)FeW(9)(OH)(3)O(34)](4-) Keggin units linked by a single edge. The terminal ligand on Fe1 in each trisubstituted Keggin unit becomes a mu(2) oxo ligand bridging to a [WO(6)](2-) moiety. The UV-vis spectra of both complexes show the characteristic oxygen-to-metal-charge-transfer bands of polyoxometalates as well as an Fe(III)-centered band at 436 nm (epsilon = 146 M(-1) cm(-1)) and 456 nm (epsilon = 104 M(-1) cm(-1)) for complexes 1 and 2, respectively. Differential scanning calorimetry data show that complex 1 decomposes between 575 and 600 degrees C whereas no decomposition is observed for complex 2 up to temperatures of 600 degrees C.
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