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_4034091
_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         'C21 H22 Cl2 N Rh'
_chemical_formula_sum            'C21 H22 Cl2 N Rh'
_chemical_formula_weight         462.20
_chemical_name_common            Cp*RhCl(4-ClPhPy)
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-06-16
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3494(2)
_cell_length_b                   15.8182(3)
_cell_length_c                   15.8765(3)
_cell_measurement_reflns_used    10453
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.1900
_cell_measurement_theta_min      3.9770
_cell_volume                     1845.71(7)
_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    -83.00  10.00   0.50    0.26    --  -49.87 103.00-122.00  186
  2  \w     12.00  83.00   0.50    0.26    --   49.87-103.00 135.00  142
  3  \w   -156.00 -81.00   0.50    1.05    --  -84.25-103.00 135.00  150
  4  \w    -85.00 -12.00   0.50    1.05    --  -84.25 103.00-122.00  146
  5  \w     34.00 110.00   0.50    1.05    --  105.75-103.00 135.00  152
  6  \w    103.00 178.00   0.50    1.05    --  105.75 103.00-122.00  150
  7  \w   -121.00 -70.00   0.50    0.26    --  -49.87-125.00 -60.00  102
  8  \w    -52.00  24.00   0.50    0.26    --  -49.87  19.00 -60.00  152
  9  \w   -121.00 -70.00   0.50    0.26    --  -49.87-125.00-180.00  102
 10  \w    -52.00 -12.00   0.50    1.05    --  -84.25  30.00  60.00   80
 11  \w     98.00 178.00   0.50    1.05    --  105.75  15.00  60.00  160
 12  \w     34.00 120.00   0.50    1.05    --  105.75 -61.00 -90.00  172
 13  \w     34.00  90.00   0.50    1.05    --  105.75 -45.00 -90.00  112
 14  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00  30.00   76
 15  \w     34.00  90.00   0.50    1.05    --  105.75 -45.00 150.00  112
 16  \w     33.00  82.00   0.50    1.05    --  105.75 -15.00-120.00   98
 17  \w     97.00 178.00   0.50    1.05    --  105.75  45.00 150.00  162
 18  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00-150.00   76
 19  \w     34.00  90.00   0.50    1.05    --  105.75 -45.00 120.00  112
 20  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00  60.00   76
 21  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00 -60.00   76
 22  \w     98.00 178.00   0.50    1.05    --  105.75  15.00  90.00  160
 23  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00  90.00   76
 24  \w     33.00  82.00   0.50    1.05    --  105.75 -15.00  90.00   98
 25  \w     34.00  72.00   0.50    1.05    --  105.75 -30.00 -90.00   76
 26  \w     29.00  62.00   0.50    0.26    --   49.87  77.00 150.00   66
 27  \w     29.00 121.00   0.50    0.26    --   49.87  77.00 -90.00  184
;
_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      0.0618907000
_diffrn_orient_matrix_UB_12      -0.0065380000
_diffrn_orient_matrix_UB_13      -0.0924411000
_diffrn_orient_matrix_UB_21      -0.1100054000
_diffrn_orient_matrix_UB_22      -0.0822588000
_diffrn_orient_matrix_UB_23      -0.0101033000
_diffrn_orient_matrix_UB_31      -0.1675242000
_diffrn_orient_matrix_UB_32      0.0515801000
_diffrn_orient_matrix_UB_33      -0.0277727000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0658
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23005
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.295
_diffrn_reflns_theta_min         3.945
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60644
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       needle
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.027
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.790
_refine_diff_density_min         -1.473
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.49(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3882
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0466
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0792P)^2^+2.6982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1340
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.729
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                3610
_reflns_number_total             3882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01716_si_002.cif
_cod_data_source_block           2e
_cod_database_code               4034091
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         RhClC24H24N2O2F2
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.191
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.51(4)
 0.49(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Rh1-Cl1 \\sim Rh1-Cl1'
 with sigma of 0.005
 Rh1-N1 \\sim Rh1-N1'
 with sigma of 0.01
 Rh1-C1 \\sim Rh1-C1'
 with sigma of 0.01
 C3-Cl2 \\sim C3'-Cl2'
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C4) = Uanis(C9') = Uanis(N1')
Uanis(C2) = Uanis(C11')
Uanis(C3) = Uanis(C10')
Uanis(C5) = Uanis(C8')
Uanis(C6) = Uanis(C7) = Uanis(C6') = Uanis(C7')
Uanis(C8) = Uanis(C5')
Uanis(C9) = Uanis(N1) = Uanis(C1') = Uanis(C4')
Uanis(C10) = Uanis(C3')
Uanis(C11) = Uanis(C2')
Uanis(Cl1) = Uanis(Cl1')
5. Same fragment restrains
{C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, N1} sigma for 1-2: 0.02, 1-3:
0.04
as
{C1', C2', C3', C4', C5', C6', C7', C8', C9', C10', C11', N1'}
6. Others
 Sof(C1')=Sof(C2')=Sof(H2')=Sof(C3')=Sof(C4')=Sof(H4')=Sof(C5')=Sof(H5')=
 Sof(C6')=Sof(C7')=Sof(C8')=Sof(H8')=Sof(C9')=Sof(H9')=Sof(C10')=Sof(H10')=
 Sof(C11')=Sof(H11')=Sof(N1')=Sof(Cl2')=Sof(Cl1')=1-FVAR(1)
 Sof(Cl1)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(H11)=Sof(N1)=Sof(Cl2)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C2'(H2'),
 C4'(H4'), C5'(H5'), C8'(H8'), C9'(H9'), C10'(H10'), C11'(H11')
7.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C)
;