Reversible Concerted Metalation-Deprotonation C-H Bond Activation by [Cp*RhCl<sub>2</sub>]<sub>2</sub>.
VanderWeide, Andrew I.; Brennessel, William W.; Jones, William D.; The Journal of organic chemistry 84 (2019) 12960–12965; doi:10.1021/acs.joc.9b01716

data_4034094
_publ_section_title
;
 Reversible Concerted Metalation-Deprotonation C-H Bond Activation by
 [Cp*RhCl<sub>2</sub>]<sub>2</sub>.
;
_journal_issue                   20
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12960
_journal_page_last               12965
_journal_paper_doi               10.1021/acs.joc.9b01716
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H29 Cl N Rh'
_chemical_formula_sum            'C24 H29 Cl N Rh'
_chemical_formula_weight         469.84
_chemical_name_common            Cp*RhCl(4-iPrPhPy)
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-27
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.4510(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.56360(10)
_cell_length_b                   7.56520(10)
_cell_length_c                   24.1880(2)
_cell_measurement_reflns_used    23110
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.2130
_cell_measurement_theta_min      3.7000
_cell_volume                     2087.27(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -65.00  21.00   0.50    0.05    --  -49.75  70.00 -48.00  172
  2  \w    -57.00 -20.00   0.50    0.17    --  -84.25  70.00 -48.00   74
  3  \w   -121.00 -58.00   0.50    0.05    --  -49.75 -38.00-150.00  126
  4  \w   -111.00 -70.00   0.50    0.05    --  -49.75-125.00 -60.00   82
  5  \w    -90.00 -56.00   0.50    0.05    --  -49.75 -70.00 179.00   68
  6  \w     84.00 121.00   0.50    0.05    --   49.75  70.00 -48.00   74
  7  \w    103.00 134.00   0.50    0.17    --  105.75  70.00 -48.00   62
  8  \w     57.00  82.00   0.50    0.17    --  105.75 -15.00 -30.00   50
  9  \w     38.00  76.00   0.50    0.17    --  105.75 -15.00  30.00   76
 10  \w     34.00  66.00   0.50    0.17    --  105.75 -30.00  30.00   64
 11  \w     44.00  69.00   0.50    0.17    --  105.75 -30.00  60.00   50
 12  \w     39.00  71.00   0.50    0.17    --  105.75 -30.00  90.00   64
 13  \w     55.00  80.00   0.50    0.17    --  105.75 -70.00 179.00   50
 14  \w     77.00 103.00   0.50    0.17    --  105.75 -77.00 120.00   52
 15  \w     34.00  68.00   0.50    0.17    --  105.75 -30.00 150.00   68
 16  \w     38.00  73.00   0.50    0.17    --  105.75 -15.00 150.00   70
 17  \w     35.00  68.00   0.50    0.17    --  105.75 -30.00 120.00   66
 18  \w     44.00  72.00   0.50    0.17    --  105.75 -77.00 120.00   56
 19  \w     36.00 120.00   0.50    0.17    --  105.75 -61.00   0.00  168
 20  \w     42.00  71.00   0.50    0.17    --  105.75 -30.00-150.00   58
 21  \w     47.00  72.00   0.50    0.17    --  105.75 -30.00-180.00   50
 22  \w     49.00  82.00   0.50    0.17    --  105.75 -15.00-180.00   66
 23  \w     43.00  68.00   0.50    0.17    --  105.75 -61.00-180.00   50
 24  \w     76.00 117.00   0.50    0.17    --  105.75 -61.00-180.00   82
 25  \w     49.00  74.00   0.50    0.17    --  105.75 -45.00-180.00   50
 26  \w     34.00  70.00   0.50    0.17    --  105.75 -30.00-120.00   72
 27  \w     36.00  65.00   0.50    0.17    --  105.75 -30.00 -60.00   58
 28  \w     41.00  67.00   0.50    0.17    --  105.75 -15.00-120.00   52
 29  \w     33.00  63.00   0.50    0.17    --  105.75 -15.00 -60.00   60
 30  \w     -1.00  24.00   0.50    0.05    --   49.75 -70.00 179.00   50
 31  \w    -43.00 -18.00   0.50    0.17    --  -84.25  30.00 150.00   50
 32  \w   -135.00-110.00   0.50    0.17    --  -84.25 -70.00 179.00   50
 33  \w   -110.00 -84.00   0.50    0.05    --  -49.87 -70.00 179.00   52
 34  \w    -91.00 -42.00   0.50    0.05    --  -49.87 -38.00-120.00   98
 35  \w    -63.00 -37.00   0.50    0.05    --  -49.87 -70.00 179.00   52
 36  \w    -18.00   8.00   0.50    0.05    --  -49.87  19.00 150.00   52
 37  \w     52.00 116.00   0.50    0.05    --   49.87  19.00  60.00  128
 38  \w    -91.00 -63.00   0.50    0.17    --  -84.25 -77.00 -90.00   56
 39  \w   -112.00 -63.00   0.50    0.17    --  -84.25 -77.00-120.00   98
 40  \w    -98.00 -72.00   0.50    0.17    --  -84.25 -77.00 -60.00   52
 41  \w     41.00  86.00   0.50    0.17    --  105.75 -45.00   0.00   90
 42  \w     92.00 144.00   0.50    0.17    --  105.75  61.00 -90.00  104
 43  \w    137.00 173.00   0.50    0.17    --  105.75  77.00-120.00   72
 44  \w    101.00 137.00   0.50    0.17    --  105.75  61.00-150.00   72
 45  \w     45.00  71.00   0.50    0.17    --  105.75 -45.00  90.00   52
 46  \w     92.00 146.00   0.50    0.17    --  105.75  61.00 -60.00  108
 47  \w     68.00  96.00   0.50    0.17    --  105.75 -94.00  30.00   56
 48  \w    141.00 168.00   0.50    0.17    --  105.75  45.00-180.00   54
 49  \w     85.00 128.00   0.50    0.17    --  105.75  77.00-120.00   86
 50  \w    138.00 164.00   0.50    0.17    --  105.75  77.00  90.00   52
 51  \w     86.00 116.00   0.50    0.17    --  105.75  77.00  90.00   60
 52  \w     98.00 142.00   0.50    0.17    --  105.75  45.00-120.00   88
 53  \w     99.00 124.00   0.50    0.17    --  105.75  45.00-150.00   50
 54  \w    102.00 137.00   0.50    0.17    --  105.75  45.00-180.00   70
 55  \w     43.00  72.00   0.50    0.17    --  105.75 -30.00   0.00   58
 56  \w     87.00 152.00   0.50    0.17    --  105.75  77.00 -90.00  130
 57  \w     94.00 146.00   0.50    0.17    --  105.75  61.00-120.00  104
 58  \w    106.00 172.00   0.50    0.17    --  105.75  15.00  90.00  132
 59  \w    112.00 137.00   0.50    0.17    --  105.75  15.00-120.00   50
;
_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      0.1161438000
_diffrn_orient_matrix_UB_12      -0.0379495000
_diffrn_orient_matrix_UB_13      -0.0211043000
_diffrn_orient_matrix_UB_21      -0.0656736000
_diffrn_orient_matrix_UB_22      -0.1188606000
_diffrn_orient_matrix_UB_23      -0.0465285000
_diffrn_orient_matrix_UB_31      -0.0211396000
_diffrn_orient_matrix_UB_32      0.1609956000
_diffrn_orient_matrix_UB_33      -0.0394432000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            35028
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.070
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.836
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85180
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow-orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.119
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.550
_refine_diff_density_min         -0.873
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.187(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         8736
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0348
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0473P)^2^+2.1903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0902
_refine_ls_wR_factor_ref         0.0907
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                8547
_reflns_number_total             8736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01716_si_002.cif
_cod_data_source_block           2h
_cod_database_code               4034094
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.456
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.813(11)
 0.187(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C36-C37 \\sim C36-C37'
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C37) = Uanis(C37')
5. Others
 Sof(H36A)=Sof(C37')=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(H36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C36(H36), C36(H36A)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C26(H26),
 C28(H28), C29(H29), C32(H32), C33(H33), C34(H34), C35(H35)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C37(H37A,
 H37B,H37C), C37'(H37D,H37E,H37F), C38(H38A,H38B,H38C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C)
;