The Mechanism of Rhodium-Catalyzed Allylic C-H Amination.
Harris, Robert J.; Park, Jiyong; Nelson, Taylor A. F.; Iqbal, Nafees; Salgueiro, Daniel C.; Bacsa, John; MacBeth, Cora E.; Baik, Mu-Hyun; Blakey, Simon B.; Journal of the American Chemical Society 142 (2020) 5842–5851; doi:10.1021/jacs.0c01069

data_4134398
_publ_section_title
;
 The Mechanism of Rhodium-Catalyzed Allylic C-H Amination.
;
_journal_issue                   12
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5842
_journal_page_last               5851
_journal_paper_doi               10.1021/jacs.0c01069
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C27 H34 N O2 Rh S'
_chemical_formula_sum            'C27 H34 N O2 Rh S'
_chemical_formula_weight         539.52
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-03
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2018.02.02 svn.r3482 for OlexSys, GUI svn.r5477)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9110(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.08450(13)
_cell_length_b                   26.7256(4)
_cell_length_c                   10.28003(15)
_cell_measurement_reflns_used    29649
_cell_measurement_temperature    102(4)
_cell_measurement_theta_max      38.2260
_cell_measurement_theta_min      2.1060
_cell_volume                     2486.71(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      102(4)
_diffrn_detector                 HyPix
_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 -42.00 -16.00 0.50 10.00 -- -22.41 -92.00 -52.00 52 2 \w -51.00 -19.00 0.50 10.00 -- -22.41 -57.00 -60.00 64 3 \w -27.00 49.00 0.50 10.00 -- 22.41 -92.00 -52.00 152 4 \w -19.00 38.00 0.50 20.00 -- 22.41 -99.00 -90.00 114 5 \w -25.00 53.00 0.50 20.00 -- 22.41 -99.00 60.00 156 6 \w -38.00 -12.00 0.50 25.00 -- -22.41 92.00 60.00 52 7 \w -91.00 -24.00 0.50 25.00 -- -22.41 -57.00 30.00 134 8 \w 52.00 93.00 0.50 25.00 -- 22.41 178.00 -60.00 82 9 \w 57.00 88.00 0.50 25.00 -- 22.41-178.00-120.00 62'
_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      0.0271237000
_diffrn_orient_matrix_UB_12      -0.0243748000
_diffrn_orient_matrix_UB_13      0.0152477000
_diffrn_orient_matrix_UB_21      0.0260915000
_diffrn_orient_matrix_UB_22      -0.0018556000
_diffrn_orient_matrix_UB_23      -0.0629201000
_diffrn_orient_matrix_UB_31      0.0687609000
_diffrn_orient_matrix_UB_32      0.0103337000
_diffrn_orient_matrix_UB_33      0.0245125000
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0333
_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       43
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44992
_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         35.630
_diffrn_reflns_theta_min         2.129
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.736
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
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    1.441
_exptl_crystal_description       plate
_exptl_crystal_F_000             1120
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and pentane  by vapor diffusion'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.931
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         11459
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0316P)^2^+0.7328P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0666
_refine_ls_wR_factor_ref         0.0689
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9946
_reflns_number_total             11459
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01069_si_004.cif
_cod_data_source_block           rjh-ii-091
_cod_depositor_comments
'Adding full bibliography for 4134397--4134399.cif.'
_cod_database_code               4134398
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C108  H136  O12  Rh4  S4  '
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.826
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_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
 C8-H8 = C7-H7
 0.999 with sigma of 0.004
 N1-H1
 0.975 with sigma of 0.004
 C7-H7 \\sim C9-H9
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uiso(H7) = Uiso(H9)
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C25(H25), C3(H3), C26(H26), C6(H6), C22(H22), C23(H23), C4(H4), C5(H5)
4.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C27(H27A,H27B,
 H27C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C10(H10A,H10B,H10C)
;
_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 RJH-II-091
_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 1.251
_oxdiff_exptl_absorpt_empirical_full_min 0.822