Investigations into the syntheses and structures of clusters of the MoOREO32− systems (E = P and As)

Abstract

The chemistry of the MoOREO32− sysems (E = P, As is remarkably diverse, exhibiting influences of the Mo oxidation state, solvent, organic substituents and reaction conditions of temperature, pressure and stoichiometry. Clusters exhibiting molybdenum nuclearities of two, four, five and six are common, as are species derived through both ligation to the Mo site and ligand-based transformations. Thus, the reactions of the Mo(VI) starting material [MoO2(acac)2] with the appropriate (REO3H2) or R′(PO3H2)2 provided a series of Mo(VI) clusters, with cyclic structures based on edge- and corner-sharing of Mo-octahedra and ligand tetrahedra. In contrast, when MoCl5 is used in the syntheses, a variety of reduced and mixed valence clusters are observed and metal-mediated ligand transformations are also common. Crystal data: (Et3NH)4[Mo4O10(C6H5PO3)4] · 2CH3CN (1): PI, a = 11.975(2), b = 12.442(2), c = 13.265(3), Å, a = 81.87(3), β = 75.24(3), γ = 65.91(3)0, V = 1743.2(9)Å3, Z = 1, R = 0.054 for 3577 independent reflections (I0 ≥ 3σ(I0)). Et3NH4)[Mo4O10 (C6H5AsO3)4] · 4H2O (2): P21ln, a = 11.243(2), b = 22.582(5), c = 14.665(3)Å, β = 108.87(2)0, V = 3523(2)Å3, Z = 2, R = 0.042 for 3412 reflections I0 ≥ 3σ(I0)). (Et3NH)4[Mo4O10{O3PCH2PO3}2] · 2CH3CH (3): P2121 a= 14.58(3), b = 17.084(3), c = 12.226(2)Å, V = 3046(2)Å3, Z = 2, R = 0.058 for 2000 reflections (I0 ≥ 3σ(I0)). (Et3NH)2[Mo4O10(CH3C6H4AsO3)2 (CH3C6H4AsO3H2] · H2) -(Et3NH)-(CH3C6H4AsO3H) (4): PI, a = 12.815(3), b = 13.668(3), c = 22.486(4)Å, a = 92.76(2), β = 93.17(2), γ = 104.62(2)c, V = 3797(2)Å, Z = 2, R = 0.051 for 5790 reflections (I0 ≥ 3σ(I0)). (Et3NH)2[Mo2O5{(C6H5)24] · CH3CN (5): PI, a = 11.102(2), b = 13.359(3), c = 22.000(4)Å, α = 85.75(2), β = 89.29(2), γ = 89.6(2)0, V = 3254(2), V = 3254(2)Å3, Z = 2, R = 0.061 for 6572 reflections I0 ≥ 3σ(I0)). (R3NH)4[Mo5O15(R′PO3)2] (R = CH2CH2CH3, R′ = −CH3) (6a): C2/c, a = 16.784(3)b = 17.855(4), c = 20.468(4)Å, β = 96.49(2)0, Z = 4, R = 0.038 for 2854 reflections (I0 ≥ 3σ(I0)). (R′ = −CH2CH3, R′ = CH2C6H5 (6b): C2/c, a = 12.915(3), b = 19.860(4), c = 21.865(4)Å, β = 102.38(2)0, V = 5433(3)Å3, Z = 4, R = 0.076 for reflections I0 ≥ 3σ(I0)). (Et3NH)4[Mo6O18-(Bu1PO3)2] · Me2CO C2/c, a = 19.982(4), b = 13.481(3), c = 22.995(5)Å, β = 112.70(2)0, V = 5716(3)Å[su3, Z = 4, R = 0.075 for 2835 reflections (I0 ≥ 3σ(I0)). (Et3NH)4 [Mo6O18(H2NC6H4AsO3)2 (8): P21/c, a = 11.243(2), b = 11.355(2), c = 22.011(4)Å, β = 99.87(1)0, V = 2764(1)Å3, Z = 2, R = 0.040 for 2198 reflections (I0 ≥ 3σ(I0). (Mo2(OH)2Cl4{MeC6H4CH2, R = 0.070 for 2478 reflections (I0 ≥ 3σ(I0)). [Mo4O8(C6H5AsO2Cl)4Cl] · [MoOCl4] · 8H2) (10) P4/nnc, a = 11.385(2), c = 37.926(8)Å, V = 4916(2)Å3, Z = 4, R = 0.056 for 981 reflections (I0 ≥ 3σ(I0). [Mo4O8(CH3C6H4AsO2 Cl4Cl] · 8CH3OH · 9H2O (11): PI, a = 10.509(2), b = 12.154(2), c = 12.461(2)Å, a = 88.09(2), β = 89.52(2), γ = 87.07(3)0, V = 1588.6(8)Å3, Z = 2, R = 0.057 for 2618 reflections (I0 ≥ 3σ(I0)).