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_4134399
_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         'C22 H29 O2 Rh'
_chemical_formula_sum            'C22 H29 O2 Rh'
_chemical_formula_weight         428.36
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-07
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2018.05.31 svn.r3508 for OlexSys, GUI svn.r5510)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.564(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2611(2)
_cell_length_b                   14.6975(3)
_cell_length_c                   18.0948(5)
_cell_measurement_reflns_used    18003
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.2650
_cell_measurement_theta_min      1.7760
_cell_volume                     1921.98(8)
_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      100(2)
_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    -25.00  55.00   0.50   10.00    --  -15.84  57.00 120.00  160
  2  \w     33.00  58.00   0.50   10.00    --  -15.84  57.00  30.00   50
  3  \w     53.00  81.00   0.50   10.00    --   15.69 178.00  60.00   56
  4  \w    -29.00  16.00   0.50   10.00    --  -15.84  57.00  30.00   90
  5  \w    -56.00  33.00   0.50   10.00    --   15.69 -57.00 -60.00  178
  6  \w      4.00  30.00   0.50   10.00    --   15.69 -99.00 -30.00   52
  7  \w     -6.00  21.00   0.50   10.00    --  -15.84 -99.00 -60.00   54
  8  \w    -24.00  21.00   0.50   10.00    --  -15.84 -99.00  30.00   90
  9  \w    -33.00  23.00   0.50   10.00    --   15.69 -95.00 103.00  112
 10  \w    -32.00  -7.00   0.50   10.00    --  -15.84 -95.00 103.00   50
 11  \w    -51.00  42.00   0.50   10.00    --   15.69 -77.00-150.00  186
 12  \w    -26.00  10.00   0.50   10.00    --  -15.84 -99.00-180.00   72
 13  \w    -47.00 -16.00   0.50   10.00    --  -15.84  95.00-146.00   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      0.0393848000
_diffrn_orient_matrix_UB_12      0.0073435000
_diffrn_orient_matrix_UB_13      -0.0338650000
_diffrn_orient_matrix_UB_21      0.0791531000
_diffrn_orient_matrix_UB_22      -0.0253854000
_diffrn_orient_matrix_UB_23      0.0136373000
_diffrn_orient_matrix_UB_31      -0.0425934000
_diffrn_orient_matrix_UB_32      -0.0403956000
_diffrn_orient_matrix_UB_33      -0.0147625000
_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  0.0581
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            36145
_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         30.508
_diffrn_reflns_theta_min         1.788
_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    0.900
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.855
_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_density_diffrn    1.480
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.555
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         5883
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0280
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0269P)^2^+0.4570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0624
_refine_ls_wR_factor_ref         0.0649
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4968
_reflns_number_total             5883
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01069_si_002.cif
_cod_data_source_block           rh-pi-allyl-complex
_cod_depositor_comments
'Adding full bibliography for 4134397--4134399.cif.'
_cod_database_code               4134399
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88  H116  O8  Rh4  '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
 C1-H1 \\sim C2-H2 \\sim C3-H3
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uiso(H2) = Uiso(H3) = Uiso(H1)
4.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C6(H6), C8(H8), C7(H7)
4.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C12(H12A,H12B,H12C), C21(H21A,H21B,
 H21C), C4(H4A,H4B,H4C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_original_sample_id Rh-pi-allyl-complex
_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 1.157
_oxdiff_exptl_absorpt_empirical_full_min 0.911