Cleavage of N-H Bond of Ammonia via Metal-Ligand Cooperation Enables Rational Design of a Conceptually New Noyori-Ikariya Catalyst.
Dub, Pavel A.; Matsunami, Asuka; Kuwata, Shigeki; Kayaki, Yoshihito; Journal of the American Chemical Society 141 (2019) 2661–2677; doi:10.1021/jacs.8b12961

data_4128178
_publ_section_title
;
 Cleavage of N-H Bond of Ammonia via Metal-Ligand Cooperation Enables
 Rational Design of a Conceptually New Noyori-Ikariya Catalyst.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2661
_journal_page_last               2677
_journal_paper_doi               10.1021/jacs.8b12961
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C30 H30 F4 Ir N3 O2 S, C2 H4 Cl2'
_chemical_formula_sum            'C32 H34 Cl2 F4 Ir N3 O2 S'
_chemical_formula_weight         863.82
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_symmetry_space_group_name_Hall  'P 4w'
_symmetry_space_group_name_H-M   'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   12.3048(11)
_cell_length_b                   12.3048(11)
_cell_length_c                   21.8820(19)
_cell_measurement_reflns_used    3901
_cell_measurement_temperature    93
_cell_measurement_theta_max      27.49
_cell_measurement_theta_min      3.25
_cell_volume                     3313.1(5)
_computing_cell_refinement       CrystalClear
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        CrystalClear
_computing_molecular_graphics    'CrystalStructure 4.2.5'
_computing_publication_material  'CrystalStructure 4.2.5 (Rigaku, 2017)'
_computing_structure_refinement  'SHELXL Version 2014/7 (Sheldrick, 2008)'
_computing_structure_solution    'SIR92 (Altomare, et al., 1994)'
_diffrn_ambient_temperature      93
_diffrn_detector_area_resol_mean 7.111
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku Saturn724'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            27342
_diffrn_reflns_point_group_measured_fraction_full 0.937
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.487
_diffrn_reflns_theta_min         3.247
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.322
_exptl_absorpt_correction_T_max  0.772
_exptl_absorpt_correction_T_min  0.574
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.732
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1704.00
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.060
_refine_diff_density_max         1.84
_refine_diff_density_min         -0.88
_refine_ls_abs_structure_details
;
 Flack x determined using 2648 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    mixed
_refine_ls_number_parameters     414
_refine_ls_number_reflns         6985
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0248
_refine_ls_R_factor_gt           0.0223
_refine_ls_shift/su_max          0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0098P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0461
_refine_ls_wR_factor_ref         0.0474
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.873
_reflns_Friedel_fraction_max     0.840
_reflns_number_gt                6444
_reflns_number_total             6985
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja8b12961_si_002.cif
_cod_data_source_block           compound7
_cod_database_code               4128178
_shelx_res_checksum              80578
_shelx_hkl_checksum              44692