Investigations into the syntheses and structures of clusters of the Mo-O-REO(3)(2-) systems (E=P and As)

The chemistry of the Mo-O-REO(3)(2-) systems (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 (REO(3)H(2)) 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: (Et(3)NH)(4)[Mo4O10(C6H5PO3)(4)]. 2CH(3)CN (1): <P(1)over bar>, a=11.975(2), b=12.442(2), c=13.265(3) Angstrom, alpha=81.87(3), beta=75.24(3), gamma= 65.91(3)degrees, V=1743.2(9) Angstrom(3), Z=1, R=0.054 for 3577 independent reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(4)[Mo4O10(C6H5AsO3)(4)]. 4H(2)O (2): P2(1)/n, a=11.243(2), b=22.582(5), c=14.665(3) Angstrom, beta=108.87(2)degrees, V=3523(2) Angstrom(3), Z=2, R=0.042 for 3412 reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(4)[Mo4O10{O3PCH2PO3}(2)]. 2CH(3)CN(3): P2(1)2(1)2, a=14.585(3), b=17.084(3), c=12.226(2) Angstrom, V=3046(2) Angstrom(3), Z=2, R=0.058 for 2000 reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(2)[Mo4O10(CH3C6H4AsO3)(2)(CH3C6H4AsO3H)(2)]. H2O .(Et(3)NH)-(CH3C6H4AsO3H) (4): <P(1)over bar>, a=12.815(3), b=13.668(3), c=22.486(4) Angstrom, alpha=92.76(2), beta=93.17(2), gamma=104.62(2)degrees, V=3797(2) Angstrom(3), Z=2, R=0.051 for 5790 reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(2)[Mo2O5{(C6H5)(2)PO2}(4)]. CH3CN (5): <P(1)over bar>, a=11.102(2), b=13.359(3), c=22.000(4) Angstrom, alpha=85.75(2), beta=89.29(2), gamma=89.96(2)degrees, V=3254(2) Angstrom(3), Z=2, R=0.061 for 6572 reflections (I-o greater than or equal to 3 sigma(I-o)). (R(3)NH)(4)[Mo5O15(R'PO3)(2)] (R=-CH2CH2CH3, R'=-CH3) (6a): C2/c, a=16.784(3), b=17.855(4), c=20.468(4) Angstrom, beta=96.49(2)degrees Z=4, R=0.038 for 2854 reflections (I-o greater than or equal to 3 sigma(I-o)). (R=-CH2CH3, R'=-CH2C6H5) (6b): C2/c, a=12.915(3), b=19.860(4), c=21.865(4) Angstrom, beta=102.38(2)degrees, V=5433(3) Angstrom(3), Z=4, R=0.076 for 2536 reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(4)[Mo6O18-(Bu(t)PO(3))(2)]. Me(2)CO (7): C2/c, a=19.982(4), b=13.481(3), c=22.999(5) Angstrom, beta=112.70(2)degrees, V=5716(3) Angstrom(3), Z=4, R=0.075 for 2835 reflections (I-o greater than or equal to 3 sigma(I-o)). (Et(3)NH)(4)[Mo6O18(H2NC6H4AsO3)(2) (8): P2(1)/c, a=11.243(2), b=11.335(2), c=22.011(4) Angstrom, beta=99.87(1)degrees, V=2764(1) Angstrom(3), Z=2, R=0.040 for 2198 reflections (I-o greater than or equal to 3 sigma(I-o)). [Mo-2(OH)(2)Cl-4{MeC(6)H(4)CH(2))P(OEt)(O)OP(O)(2)(CH(2)C(6)H(4)Me}(2)]. MeOH (9): <P(1)over bar>, a=8.650(2), b=11.486(2), c=13.684(3) Angstrom, alpha=98.44(2), beta=105.25(2), gamma=100.37(2)degrees, V=1263.0(6) Angstrom(3), Z=1, R=0.070 for 2478 reflections (I-o greater than or equal to 3 sigma(I-o)). [Mo4O8(C6H5AsO2Cl)(4)Cl].[MoOCl4]. 8H(2)O (10): P4/nnc, a=11.385(2), c=37.926(8) Angstrom, V=4916(2) Angstrom(3), Z=4, R=0.056 for 981 reflections (I-o greater than or equal to 3 sigma(I-o)). [Mo4O8(CH3C6H4AsO2Cl)(4)Cl]. 8CH(3)OH . 9H(2)O (11): 14, a=11.879(2), c=20.466(4) Angstrom, V=2888(1) Angstrom(3), Z=2, R=0.062 for 968 reflections (I-o greater than or equal to 3 sigma(I-o)). [H(3)NC(6)H(4)ASCl(3)][Mo2O2Cl7](2) (12): <P(1)over bar>, a=10.509(2), b=12.154(2), c=12.461(2) Angstrom, alpha=88.09(2), beta=89.52(2), gamma=87.07(3)degrees, V=1588.6(8) Angstrom(3), Z=2, R=0.057 for 2618 reflections (I-o greater than or equal to 3 sigma(I-o)).