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_4134397
_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         'C20 H26 Cl Rh'
_chemical_formula_sum            'C20 H26 Cl Rh'
_chemical_formula_weight         404.77
_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'
_atom_sites_solution_hydrogens   difmap
_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                 94.110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.4511(10)
_cell_length_b                   12.8249(10)
_cell_length_c                   18.6937(10)
_cell_measurement_reflns_used    85788
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      46.4160
_cell_measurement_theta_min      1.5870
_cell_volume                     1781.8(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      100.02(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 0.997
_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     10.00  36.00   0.50    5.00    --   43.57 -57.00  90.00   52
  2  \w     -3.00  75.00   0.50    5.00    --   43.57 -99.00   0.00  156
  3  \w     23.00  53.00   0.50    5.00    --   43.57-106.00 -31.00   60
  4  \w     14.00  40.00   0.50   15.00    --   43.57 -19.00   0.00   52
  5  \w     76.00 102.00   0.50   15.00    --   43.57  38.00  30.00   52
  6  \w     35.00 111.00   0.50   15.00    --   43.57  57.00   0.00  152
  7  \w     56.00 116.00   0.50   15.00    --   43.57  77.00 -90.00  120
  8  \w     50.00 117.00   0.50   15.00    --   43.57  19.00-180.00  134
  9  \w     36.00 112.00   0.50   15.00    --   43.57  38.00-180.00  152
 10  \w     24.00 116.00   0.50   15.00    --   43.57  77.00  30.00  184
 11  \w     50.00 108.00   0.50   15.00    --   43.57 178.00 -60.00  116
 12  \w     70.00 112.00   0.50   15.00    --   43.57 178.00-180.00   84
 13  \w     25.00  77.00   0.50   15.00    --   43.57  77.00  60.00  104
 14  \w     79.00 113.00   0.50   15.00    --   43.57 178.00  90.00   68
 15  \w     71.00  97.00   0.50   15.00    --   43.57 178.00 150.00   52
 16  \w     40.00  66.00   0.50   15.00    --   43.57 178.00 120.00   52
 17  \w    -77.00 -34.00   0.50   15.00    --  -43.26 106.00  67.00   86
 18  \w    -18.00   8.00   0.50   15.00    --   43.57 -38.00 150.00   52
 19  \w    -26.00  24.00   0.50   15.00    --   43.57 -57.00 120.00  100
 20  \w    -28.00   4.00   0.50   15.00    --   43.57 -38.00   0.00   64
 21  \w    -28.00  12.00   0.50   15.00    --   43.57 -19.00   0.00   80
 22  \w    -24.00  45.00   0.50   15.00    --   43.57 -57.00-120.00  138
 23  \w    -14.00  11.00   0.50   15.00    --   43.57 -38.00-150.00   50
 24  \w    -86.00 -61.00   0.50   15.00    --  -43.26-178.00-120.00   50
 25  \w     49.00 115.00   0.50   15.00    --   43.57-178.00 120.00  132
;
_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      -0.0352128000
_diffrn_orient_matrix_UB_12      0.0508012000
_diffrn_orient_matrix_UB_13      0.0043905000
_diffrn_orient_matrix_UB_21      0.0405020000
_diffrn_orient_matrix_UB_22      0.0167270000
_diffrn_orient_matrix_UB_23      -0.0312197000
_diffrn_orient_matrix_UB_31      -0.0789171000
_diffrn_orient_matrix_UB_32      -0.0140893000
_diffrn_orient_matrix_UB_33      -0.0212874000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0215
_diffrn_reflns_av_unetI/netI     0.0113
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            119524
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         46.218
_diffrn_reflns_theta_min         1.927
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.103
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.564
_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    1.509
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and pentane  by vapor diffusion'
_exptl_crystal_size_max          0.367
_exptl_crystal_size_mid          0.319
_exptl_crystal_size_min          0.278
_refine_diff_density_max         1.343
_refine_diff_density_min         -1.100
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.197
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         15581
_refine_ls_number_restraints     317
_refine_ls_restrained_S_all      1.186
_refine_ls_R_factor_all          0.0221
_refine_ls_R_factor_gt           0.0201
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0153P)^2^+0.5675P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0477
_refine_ls_wR_factor_ref         0.0482
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14700
_reflns_number_total             15581
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01069_si_003.cif
_cod_data_source_block           rh-p-allyl-cl
_cod_depositor_comments
'Adding full bibliography for 4134397--4134399.cif.'
_cod_database_code               4134397
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80  H104  Cl4  Rh4  '
_reflns_odcompleteness_completeness 98.22
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     46.37
_olex2_refinement_description
;
1. Restrained distances
 C8-H8A \\sim C9-H9A \\sim C9-H9B \\sim C9-H9C \\sim C8-H8B \\sim C8-H8C \\sim
C10-H10A \\sim C10-H10B ~
 C10-H10C \\sim C6-H6A \\sim C6-H6B \\sim C6-H6C \\sim C7-H7A \\sim C7-H7B
\\sim C7-H7C
 with sigma of 0.002
 H9B-H9A \\sim H9C-H9A \\sim H9C-H9B \\sim H8B-H8A \\sim H8C-H8A \\sim H8C-H8B
\\sim H10B-H10A \\sim H10C-
 H10A \\sim H10C-H10B \\sim H6B-H6A \\sim H6C-H6A \\sim H6C-H6B \\sim H7C-H7A
\\sim H7B-H7A \\sim H7C-H7B
 with sigma of 0.005
 C14-H14C \\sim C14-H14B \\sim C14-H14A \\sim C10-H10A
 with sigma of 0.002
 H9B-H9A \\sim H14C-H14B
 with sigma of 0.005
 H14C-H14A \\sim H14B-H14A \\sim H14C-H14B
 with sigma of 0.005
 C20-H20 \\sim C19-H19 \\sim C18-H18 \\sim C17-H17 \\sim C16-H16
 with sigma of 0.002
 C11-H11 \\sim C13-H13
 with sigma of 0.002
2. Uiso/Uaniso restraints and constraints
Uiso(H9C) = Uiso(H10C) = Uiso(H6C) = Uiso(H7A) = Uiso(H8C)
Uiso(H9A) = Uiso(H9C) = Uiso(H9B)
Uiso(H7C) = Uiso(H8B) = Uiso(H8A) = Uiso(H9A) = Uiso(H9B) = Uiso(H10A) =
Uiso(H10B) = Uiso(H7B) = Uiso(H6B)
Uiso(H14C) = Uiso(H14A) = Uiso(H14B)
Uiso(H20) = Uiso(H16)
Uiso(H19) = Uiso(H17) = Uiso(H18)
Uiso(H11) = Uiso(H13)
;
_shelx_res_checksum              29520
_shelx_hkl_checksum              55948
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_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 1.086
_oxdiff_exptl_absorpt_empirical_full_min 0.911