Bismuth-Substituted “Sandwich” Type Polyoxometalate Catalyst for Activation of Peroxide: Umpolung of the Peroxo Intermediate and Change of Chemoselectivity
Amanchi, Srinivasa Rao; Khenkin, Alexander M.; Diskin-Posner, Yael; Neumann, Ronny; ACS Catalysis 5 (2015) 3336–; doi:10.1021/acscatal.5b00066

data_4512948
_publ_section_title
;
 Bismuth-Substituted &#x201C;Sandwich&#x201D; Type Polyoxometalate
 Catalyst for Activation of Peroxide: Umpolung of the Peroxo Intermediate
 and Change of Chemoselectivity
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3336
_journal_paper_doi               10.1021/acscatal.5b00066
_journal_volume                  5
_journal_year                    2015
_chemical_formula_moiety         'Bi2 O68 W18 Zn4, 2(O2 Zn), 26.56(O), 4(Na)'
_chemical_formula_sum            'Bi2 Na4 O98.55 W18 Zn6'
_chemical_formula_weight         5788.24
_space_group_crystal_system      orthorhombic
_space_group_IT_number           58
_space_group_name_Hall           '-P 2 2n'
_space_group_name_H-M_alt        'P n n m'
_symmetry_space_group_name_Hall  '-P 2 2n'
_symmetry_space_group_name_H-M   'P n n m'
_audit_creation_method           SHELXL-2014/6
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.187(3)
_cell_length_b                   19.430(4)
_cell_length_c                   14.641(3)
_cell_measurement_reflns_used    9100
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      26.37
_cell_measurement_theta_min      1.98
_cell_volume                     4604.8(16)
_computing_cell_refinement       HKL
_computing_data_collection       'Collect package Nonius'
_computing_data_reduction        HKL
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      120(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_laue_measured_fraction_full 0.994
_diffrn_reflns_laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            4891
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.369
_diffrn_reflns_theta_min         3.388
_exptl_absorpt_coefficient_mu    27.850
_exptl_absorpt_correction_T_max  0.3365
_exptl_absorpt_correction_T_min  0.1496
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'Nonius KappaCCD'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    4.175
_exptl_crystal_description       prism
_exptl_crystal_F_000             5021
_exptl_crystal_size_max          0.110
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.050
_refine_diff_density_max         2.586
_refine_diff_density_min         -3.480
_refine_diff_density_rms         0.368
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         4891
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.022
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0669P)^2^+90.1528P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1119
_refine_ls_wR_factor_ref         0.1153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4243
_reflns_number_total             4891
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5b00066_si_002.cif
_cod_data_source_block           n421
_cod_depositor_comments
'Adding full bibliography for 4512947--4512948.cif.'
_cod_database_code               4512948
_shelx_estimated_absorpt_t_min   0.150
_shelx_estimated_absorpt_t_max   0.336
_shelxl_version_number           2014/6
_shelx_res_checksum              42917
_shelx_hkl_checksum              48709