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_4512947
_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         '2(Bi2 O69 W18 Zn4), 75.36(O), 20.72(Na)'
_chemical_formula_sum            'Bi4 Na20.72 O213.36 W36 Zn8'
_chemical_formula_weight         11867.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_audit_creation_method           SHELXL-2014/6
_cell_angle_alpha                90
_cell_angle_beta                 93.12(3)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   13.234(3)
_cell_length_b                   17.661(4)
_cell_length_c                   20.966(4)
_cell_measurement_reflns_used    86964
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.74
_cell_measurement_theta_min      2.912
_cell_volume                     4893.0(18)
_computing_cell_refinement       APEX2
_computing_data_collection       'Collect package Bruker'
_computing_data_reduction        APEX2
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX - II KappaCCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0610
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            85156
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.787
_diffrn_reflns_theta_min         1.946
_exptl_absorpt_coefficient_mu    25.771
_exptl_absorpt_correction_T_max  0.4254
_exptl_absorpt_correction_T_min  0.0462
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker APEX2'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    4.028
_exptl_crystal_description       plate
_exptl_crystal_F_000             5164
_exptl_crystal_size_max          0.310
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.040
_refine_diff_density_max         2.992
_refine_diff_density_min         -2.548
_refine_diff_density_rms         0.365
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     749
_refine_ls_number_reflns         12704
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0401
_refine_ls_shift/su_max          0.035
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0501P)^2^+85.6220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0985
_refine_ls_wR_factor_ref         0.1096
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10123
_reflns_number_total             12704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5b00066_si_003.cif
_cod_data_source_block           n459
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/usr/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 3271 2015-04-21 07:52:19Z andrius 

 Adding full bibliography for 4512947--4512948.cif.
;
_cod_original_cell_volume        4893.0(17)
_cod_database_code               4512947
_shelx_estimated_absorpt_t_min   0.046
_shelx_estimated_absorpt_t_max   0.425
_shelxl_version_number           2014/6
_shelx_res_checksum              26591
_shelx_hkl_checksum              93089