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_4034090
_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_formula_moiety         'C22 H22 Cl F3 N Rh'
_chemical_formula_sum            'C22 H22 Cl F3 N Rh'
_chemical_formula_weight         495.76
_chemical_name_common            Cp*RhCl(4-CF3PhPy)
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-05-09
_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                 92.5580(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.45080(10)
_cell_length_b                   7.71430(10)
_cell_length_c                   16.50760(10)
_cell_measurement_reflns_used    18906
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.4430
_cell_measurement_theta_min      2.6960
_cell_volume                     1965.62(3)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -81.00  22.00   0.50    0.05    --  -49.75  99.00 -71.00  206
  2  \w     -4.00  81.00   0.50    0.05    --   49.75 -99.00-177.00  170
  3  \w   -156.00 -83.00   0.50    0.05    --  -84.25 -99.00-177.00  146
  4  \w    104.00 178.00   0.50    0.05    --  105.75  99.00 -71.00  148
  5  \w    -57.00  22.00   0.50    0.05    --  -49.75  38.00 -30.00  158
  6  \w   -121.00 -70.00   0.50    0.05    --  -49.75-125.00-120.00  102
  7  \w    -52.00 -12.00   0.50    0.05    --  -84.25  30.00 150.00   80
  8  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00-180.00   76
  9  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00 -60.00   76
 10  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00-120.00   76
 11  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00-150.00   76
 12  \w     34.00  90.00   0.50    0.05    --  105.75 -45.00-180.00  112
 13  \w     33.00  82.00   0.50    0.05    --  105.75 -15.00 -30.00   98
 14  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00   0.00   76
 15  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00  90.00   76
 16  \w     34.00  72.00   0.50    0.05    --  105.75 -30.00 -30.00   76
 17  \w     34.00 116.00   0.50    0.05    --  105.75-125.00-180.00  164
 18  \w     33.00  82.00   0.50    0.05    --  105.75 -15.00  30.00   98
 19  \w     98.00 178.00   0.50    0.05    --  105.75  30.00-150.00  160
 20  \w     33.00  82.00   0.50    0.05    --  105.75 -15.00 120.00   98
 21  \w     34.00  90.00   0.50    0.05    --  105.75 -45.00  60.00  112
 22  \w     33.00  82.00   0.50    0.05    --  105.75 -15.00 -60.00   98
 23  \w     34.00  90.00   0.50    0.05    --  105.75 -45.00 -90.00  112
 24  \w     97.00 178.00   0.50    0.05    --  105.75  45.00-150.00  162
 25  \w     34.00 109.00   0.50    0.05    --  105.75 -99.00-177.00  150
 26  \w     29.00 121.00   0.50    0.05    --   49.75  77.00 150.00  184
 27  \w     29.00 121.00   0.50    0.05    --   49.75  77.00  60.00  184
 28  \w     29.00 107.00   0.50    0.05    --   49.75  77.00-120.00  156
 29  \w     29.00 121.00   0.50    0.05    --   49.75  77.00 -30.00  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      -0.0627771000
_diffrn_orient_matrix_UB_12      -0.1077741000
_diffrn_orient_matrix_UB_13      0.0496218000
_diffrn_orient_matrix_UB_21      0.0653910000
_diffrn_orient_matrix_UB_22      0.0040468000
_diffrn_orient_matrix_UB_23      0.0731874000
_diffrn_orient_matrix_UB_31      -0.0417574000
_diffrn_orient_matrix_UB_32      0.1681657000
_diffrn_orient_matrix_UB_33      0.0300365000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0415
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25826
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.792
_diffrn_reflns_theta_min         2.863
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.587
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22493
_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    1.675
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.889
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4140
_refine_ls_number_restraints     109
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0266
_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^)+(0.0349P)^2^+2.4524P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0685
_refine_ls_wR_factor_ref         0.0689
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4059
_reflns_number_total             4140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01716_si_002.cif
_cod_data_source_block           2c
_cod_database_code               4034090
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         RhClNC24H24F3
_shelx_estimated_absorpt_t_max   0.539
_shelx_estimated_absorpt_t_min   0.268
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C3-C12 \\sim C3-C12' \\sim C3-C12"
 with sigma of 0.01
 C12-F1 \\sim C12-F2 \\sim C12-F3 \\sim C12-F1' \\sim C12-F2' \\sim C12-F3'
\\sim C12"-F1" \\sim C12"-F2"
 \\sim C12"-F3"
 with sigma of 0.01
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1'-F2' \\sim F2'-F3' \\sim F3'-F1' \\sim
F1"-F2" \\sim F2"-F3" \\sim F3"-
 F1"
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1 \\sim F1' \\sim F1": within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
F2 \\sim F2' \\sim F2": within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
F3 \\sim F3' \\sim F3": within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(F1") = Uanis(F3')
Uanis(F1') = Uanis(F2")
Uanis(F2') = Uanis(F3")
Uanis(C12) = Uanis(C12') = Uanis(C12")
4. Others
 1*[Sof(F3)+Sof(F1)+Sof(F2)+Sof(C12)]+1*[Sof(F1')+Sof(F2')+Sof(F3')+Sof(C12')]+
 1*[Sof(F2")+Sof(F1")+Sof(F3")+Sof(C12")]=1 with esd of 0.0001
 Sof(F3)=Sof(F1)=Sof(F2)=Sof(C12)=FVAR(1)
 Sof(F1')=Sof(F2')=Sof(F3')=Sof(C12')=FVAR(2)
 Sof(F2")=Sof(F1")=Sof(F3")=Sof(C12")=FVAR(3)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11)
5.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C)
;