118682-03-4Relevant articles and documents
Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [n-Bu4N]2[Mo4O10(OMe) 4X2] (X = -OMe, -Cl) and their relationship to the catecholate derivative [n-Bu4N]2[Mo4O ...
Kang, Hyunkyu,Liu, Shuncheng,Shaikh, Shahid N.,Nicholson, Terrence,Zubieta, Jon
, p. 920 - 933 (2008/10/08)
Full title: Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [n-Bu4N]2[Mo4O10(OMe) 4X2] (X = -OMe, -Cl) and their relationship to the catecholate derivative [n-Bu4N]2[Mo4O10(OMe) 2(OC6H4O)2] and to the diazenido complexes of the o-aminophenolate and the naphthalene-2,3-diolate derivatives [n-Bu4N]2[Mo4O6(OMe) 2(HNC6H4O)2(NNC6H 5)4] and [n-Bu4N]2[Mo4O6(OMe) 2(C10H6O2)2(NNC 6H5)4]. Comparison to the structure of a binuclear complex with the [Mo2(OMe)2(NNC6H5)4] 2+ core, [Mo2(OMe)2(H2NC6H4O) 2(NNC6H5)4]. The tetranuclear methoxooxomolybdate [MePPh3]2[Mo4O10(OCH 3)6] ([MePPh3]2[I]) provides a synthetic precursor and a structural prototype for a class of tetranuclear polyoxomolybdate coordination complexes. Reaction of I with Me3SiCl yields [Mo4O10(OCH3)4Cl2] 2- (II), which in turn may be reduced by thiols to yield a mixed-valence Mo(VI)/Mo(V) species, [n-Bu4N]2[Mo4O8(OCH 3)4Cl4] ([n-Bu4N]2[III]). In the presence of chelating ligands, I reacts to give tetranuclear derivatives of the class [n-Bu4N]2[Mo4O10(OCH 3)2(LL)2], where LL = catecholate ([n-Bu4N]2[IVa]), 3-tert-butylcatecholate ([n-Bu4N]2[IVb]), naphthalene-2,3-diolate ([n-Bu4N]2[IVc]), o-aminophenolate ([n-Bu4N]2[IVd]). Peripheral oxo groups of complexes IVa-d may be replaced by diazenido groups in condensation type reactions to give the tetranuclear complexes [n-Bu4N]2[Mo4O6(OCH 3)2(LL)2(NNC6H5) 4] ([n-Bu4N]2[Va-d]). The related binuclear class of complexes [Mo2(OCH3)2(NNC6H5) 4(LL)2]n (VIa-d) has also been synthesized. Crystal data: I, triclinic, space group P1, a = 10.185 (2) ?, b = 10.848 (2) ?, c = 11.686 (2) ? α = 92.55 (2)°, β = 107.15 (2)°, γ = 96.79 (2)°, V = 1220.8 (6) ?3, Z = 1, 2798 reflections (Mo Kα, λ = 0.71073 ? in all cases), R = 0.0246; II, triclinic, space group P1, a = 10.186 (4) ?, b = 11.722 (3) ?, c = 13.173 (4) ?, α = 109.35 (2)°, β = 107.43 (1)°, γ = 96.99 (1)°, V = 1372.6 (6) ?3, Z = 1, 3020 reflections, R = 0.0407; III, monoclinic, space group P21/n, a = 10.653 (3) ?, b = 13.184 (4) ?, c = 12.703 (4) ?, β = 98.12 (1)°, V = 1766.1 (8) ?3, Z = 2, 2424 reflections, R = 0.0469; IVa, monoclinic, space group P21/a, a = 18.494 (3) ?, b = 16.192 (4) ?, c = 20.411 (3) ?, β = 107.51 (1)°, V = 5822.6 (10) ?3, Z = 4, 3832 reflections, R = 0.0566; Vc, rhombohedral, space group R3 (hexagonal indices), a = 26.609 (4) ?, c = 31.844 (7) ?, V = 19519.4 (9) ?3, Z = 9, 2730 reflections, R = 0.0616; Vd, monoclinic, space group P21/n, a = 24.675 (2) ?, b = 19.937 (3) ?, c = 17.295 (4) ?, β = 112.62 (2)°, V = 7854.3 (11) ?, Z = 4, 4015 reflections, R = 0.0781; VId, triclinic, space group P1, a = 9.500 (2) ?, b = 11.942 (3) ?, c = 12.026 (2) ?, α = 61.94 (1)°, β = 81.80 (2)°, γ = 86.11 (2)°, V = 1191.7 (10) ?3, Z = 1, 2059 reflections, R = 0.0441.
