Rh(III) and Ir(III)Cp* Complexes Provide Complementary Regioselectivity Profiles in Intermolecular Allylic C‒H Amidation Reactions
Burman, Jacob S.; Harris, Robert J.; B. Farr, Caitlin M.; Bacsa, John; Blakey, Simon B.; ACS Catalysis 9 (2019) 5474–; doi:10.1021/acscatal.9b01338

data_4514413
_publ_section_title
;
 Rh(III) and Ir(III)Cp* Complexes Provide Complementary Regioselectivity
 Profiles in Intermolecular Allylic C--H Amidation Reactions
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              5474
_journal_paper_doi               10.1021/acscatal.9b01338
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C20 H26 Cl Ir'
_chemical_formula_sum            'C20 H26 Cl Ir'
_chemical_formula_weight         494.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-18
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.9187(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.46343(7)
_cell_length_b                   12.81878(13)
_cell_length_c                   18.68909(19)
_cell_measurement_reflns_used    58508
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      46.3060
_cell_measurement_theta_min      1.9020
_cell_volume                     1783.84(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -35.00 -10.00   0.50    5.00    --  -43.26  33.00 -51.00   50
  2  \w     45.00  95.00   0.50    5.00    --   43.57  33.00 -51.00  100
  3  \w     77.00 117.00   0.50    5.00    --   43.57  19.00 -90.00   80
  4  \w     78.00 112.00   0.50    5.00    --   43.57  57.00   0.00   68
  5  \w     63.00 116.00   0.50    5.00    --   43.57  57.00  60.00  106
  6  \w     48.00  85.00   0.50    5.00    --   43.57  57.00 120.00   74
  7  \w     32.00  70.00   0.50    5.00    --   43.57  57.00  90.00   76
  8  \w     36.00  91.00   0.50    5.00    --   43.57  38.00  90.00  110
  9  \w     24.00 104.00   0.50    5.00    --   43.57  75.00 115.86  160
 10  \w     58.00  84.00   0.50    5.00    --   43.57 178.00  90.00   52
 11  \w     89.00 116.00   0.50    5.00    --   43.57 178.00  90.00   54
 12  \w     32.00  72.00   0.50    5.00    --   43.57  57.00   0.00   80
 13  \w     36.00  61.00   0.50    5.00    --   43.57  38.00 -60.00   50
 14  \w     47.00  73.00   0.50    5.00    --   43.57  38.00-150.00   52
 15  \w      3.00  29.00   0.50    5.00    --   43.57 -19.00-180.00   52
 16  \w     15.00  46.00   0.50    5.00    --   43.57 -57.00-180.00   62
 17  \w    -27.00  26.00   0.50    5.00    --   43.57 -57.00-150.00  106
 18  \w    -27.00  17.00   0.50    5.00    --   43.57 -57.00 -30.00   88
 19  \w     21.00  64.00   0.50    5.00    --   43.57 -77.00  30.00   86
 20  \w     15.00  41.00   0.50    5.00    --   43.57 -57.00 120.00   52
 21  \w     12.00  38.00   0.50    5.00    --   43.57 -77.00  60.00   52
 22  \w     17.00  43.00   0.50    5.00    --   43.57 -57.00  30.00   52
 23  \w     -5.00  41.00   0.50    5.00    --   43.57 -57.00  90.00   92
 24  \w    -16.00  40.00   0.50    5.00    --   43.57 -33.00 149.00  112
 25  \w    -19.00   7.00   0.50    5.00    --   43.57 -77.00  30.00   52
 26  \w    -18.00  28.00   0.50    5.00    --   43.57 -38.00   0.00   92
 27  \w    -26.00   8.00   0.50    5.00    --   43.57 -57.00 120.00   68
 28  \w     36.00 106.00   0.50    5.00    --   43.57-178.00   0.00  140
 29  \w    -99.00 -74.00   0.50    5.00    --  -43.26 -33.00 149.00   50
 30  \w     67.00  92.00   0.50    5.00    --   43.57 178.00-150.00   50
 31  \w    -91.00 -62.00   0.50    5.00    --  -43.26-178.00 -90.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0761449000
_diffrn_orient_matrix_UB_12      -0.0153298000
_diffrn_orient_matrix_UB_13      0.0181119000
_diffrn_orient_matrix_UB_21      -0.0423216000
_diffrn_orient_matrix_UB_22      -0.0177955000
_diffrn_orient_matrix_UB_23      -0.0328451000
_diffrn_orient_matrix_UB_31      0.0383960000
_diffrn_orient_matrix_UB_32      -0.0500420000
_diffrn_orient_matrix_UB_33      0.0061029000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0530
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            115550
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         44.169
_diffrn_reflns_theta_min         1.928
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.629
_exptl_absorpt_correction_T_max  0.761
_exptl_absorpt_correction_T_min  0.238
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.840
_exptl_crystal_description       block
_exptl_crystal_F_000             960
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and pentane  by vapor diffusion'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.225
_refine_diff_density_max         3.798
_refine_diff_density_min         -3.782
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     205
_refine_ls_number_reflns         14094
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0290
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0234P)^2^+2.3397P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0622
_refine_ls_wR_factor_ref         0.0641
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12230
_reflns_number_total             14094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01338_si_002.cif
_cod_data_source_block           ir-cl-allyl
_cod_depositor_comments
'Adding full bibliography for 4514412--4514413.cif.'
_cod_original_cell_volume        1783.85(3)
_cod_database_code               4514413
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H25 N25 O25 Ir25 Cl'
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     46.37
_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.a Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C13(H13)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C),
 C6(H6A,H6B,H6C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              94518
_shelx_hkl_checksum              54575
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id Ir-Cl-allyl
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.802