Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides.
Klet, Rachel C.; Kaphan, David M.; Liu, Cong; Yang, Ce; Kropf, A. Jeremy; Perras, Frédéric A; Pruski, Marek; Hock, Adam S.; Delferro, Massimiliano; Journal of the American Chemical Society 140 (2018) 6308–6316; doi:10.1021/jacs.8b00995

data_4132047
_publ_section_title
;
 Evidence for Redox Mechanisms in Organometallic Chemisorption and
 Reactivity on Sulfated Metal Oxides.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6308
_journal_page_last               6316
_journal_paper_doi               10.1021/jacs.8b00995
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C20 H31 Ir P, B C24 F20, C H2 Cl2'
_chemical_formula_sum            'C45 H33 B Cl2 F20 Ir P'
_chemical_formula_weight         1258.59
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                74.683(3)
_cell_angle_beta                 80.155(3)
_cell_angle_gamma                83.512(3)
_cell_formula_units_Z            2
_cell_length_a                   10.1418(5)
_cell_length_b                   14.6984(8)
_cell_length_c                   15.9199(9)
_cell_measurement_reflns_used    9505
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.76
_cell_measurement_theta_min      2.68
_cell_volume                     2249.4(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.05
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0429
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            64743
_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         36.400
_diffrn_reflns_theta_min         2.200
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    3.240
_exptl_absorpt_correction_T_max  0.1661
_exptl_absorpt_correction_T_min  0.1158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0602 before and 0.0495 after correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.858
_exptl_crystal_description       plate
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.107
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.016
_refine_diff_density_max         2.089
_refine_diff_density_min         -1.690
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         21849
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0413
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0318P)^2^+2.5718P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0875
_refine_ls_wR_factor_ref         0.0908
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18833
_reflns_number_total             21849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b00995_si_003.cif
_cod_data_source_block           dmka2
_cod_database_code               4132047
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.723
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Others
 Sof(Ir1A)=Sof(H6BC)=Sof(H6BD)=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(1)
 Sof(Ir1)=Sof(H6AA)=Sof(H6AB)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B)
3.b Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C11(H11D,H11E,H11F)
3.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17)
3.d X=CH2 refined with riding coordinates:
 C6(H6AA,H6AB), C6(H6BC,H6BD)
3.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              81050
_shelx_hkl_checksum              51322
_olex2_date_sample_data_collection 2017-06-06
_olex2_date_sample_submission    2017-06-05
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id dmka2
_olex2_submission_special_instructions 'No special instructions were received'