Base-Promoted, Remote C-H Activation at a Cationic (η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(III) Center Involving Reversible C-C Bond Formation of Bound C<sub>5</sub>Me<sub>5</sub>.
Moreno, Juan J.; Espada, María F; Campos, Jesús; López-Serrano, Joaquín; Macgregor, Stuart A.; Carmona, Ernesto; Journal of the American Chemical Society 141 (2019) 2205–2210; doi:10.1021/jacs.8b11752

data_4128214
_publ_section_title
;
 Base-Promoted, Remote C-H Activation at a Cationic
 (\h<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(III) Center Involving
 Reversible C-C Bond Formation of Bound C<sub>5</sub>Me<sub>5</sub>.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2205
_journal_page_last               2210
_journal_paper_doi               10.1021/jacs.8b11752
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H42 Cl Ir P, C32 H12 B F24'
_chemical_formula_sum            'C66 H54 B Cl F24 Ir P'
_chemical_formula_weight         1572.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-02-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.8980(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   12.8963(5)
_cell_length_b                   19.5146(8)
_cell_length_c                   13.2343(5)
_cell_measurement_reflns_used    9783
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      33.49
_cell_measurement_theta_min      2.33
_cell_volume                     3306.5(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0195
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            58010
_diffrn_reflns_theta_full        25.25
_diffrn_reflns_theta_max         25.25
_diffrn_reflns_theta_min         2.08
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.191
_exptl_absorpt_correction_T_max  0.7470
_exptl_absorpt_correction_T_min  0.5594
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0944 before and 0.0706 after correction.
The Ratio of minimum to maximum transmission is 0.7489.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.579
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1560
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.833
_refine_diff_density_min         -0.359
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.003(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     875
_refine_ls_number_reflns         11634
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0227
_refine_ls_R_factor_gt           0.0217
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0226P)^2^+2.1442P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0565
_refine_ls_wR_factor_ref         0.0572
_reflns_number_gt                11311
_reflns_number_total             11634
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8b11752_si_003.cif
_cod_data_source_block           mf01115a_0m
_cod_database_code               4128214
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C74-F23A \\sim C74-F23B \\sim C74-F24A \\sim C74-F24B \\sim C74-F25A \\sim
C74-F25B
 with sigma of 0.02
 F24A-F24B \\sim F24B-F23A \\sim F23A-F23B \\sim F23B-F25A \\sim F25A-F25B
\\sim F25B-F24A
 with sigma of 0.02
3. Rigid bond restraints
 F23A, F24A, F25A, F23B, F24B, F25B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
F23A \\sim F24A \\sim F25A \\sim F23B \\sim F24B \\sim F25B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(F23B)=Sof(F24B)=Sof(F25B)=1-FVAR(1)
 Sof(F23A)=Sof(F24A)=Sof(F25A)=FVAR(1)
6.a Me refined with riding coordinates:
 C36(H36A,H36B,H36C), C33(H33A,H33B,H33C), C46(H46A,H46B,H46C), C48(H48A,H48B,
 H48C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C), C49(H49A,H49B,H49C), C45(H45A,
 H45B,H45C), C47(H47A,H47B,H47C), C44(H44A,H44B,H44C), C71(H71A,H71B,H71C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C1(H1), C14(H14), C6(H6), C8(H8), C17(H17), C9(H9), C22(H22),
 C11(H11), C38(H38), C30(H30), C32(H32), C42(H42), C43(H43), C63(H63), C57(H57),
  C60(H60), C70(H70), C79(H79), C77(H77), C78(H78)
;
_olex2_submission_special_instructions 'No special instructions were received'