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_4034092
_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 N2 Rh, C3 H3'
_chemical_formula_sum            'C25 H25 Cl N2 Rh'
_chemical_formula_weight         491.83
_chemical_name_common            Cp*RhCl(4-CNPhPy)
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-12
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                92.1070(10)
_cell_angle_beta                 106.3890(10)
_cell_angle_gamma                103.3290(10)
_cell_formula_units_Z            2
_cell_length_a                   7.91950(10)
_cell_length_b                   12.04280(10)
_cell_length_c                   12.33690(10)
_cell_measurement_reflns_used    21920
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.0290
_cell_measurement_theta_min      3.7460
_cell_volume                     1091.84(2)
_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 0.998
_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    -77.00  20.00   0.50    0.05    --  -49.62  96.00  14.00  194
  2  \w     -7.00  79.00   0.50    0.05    --   49.62 -96.00 -94.00  172
  3  \w   -123.00 -98.00   0.50    0.05    --  -84.25 -96.00 -94.00   50
  4  \w    -72.00 -47.00   0.50    0.05    --  -84.25  96.00  14.00   50
  5  \w     69.00 109.00   0.50    0.05    --  105.75 -96.00 -94.00   80
  6  \w    138.00 164.00   0.50    0.05    --  105.75  96.00  14.00   52
  7  \w    -43.00 -14.00   0.50    0.05    --    4.00 130.00 169.16   58
  8  \w    -51.00 -25.00   0.50    0.05    --   12.00 154.00 -56.58   52
  9  \w    -14.00  15.00   0.50    0.05    --   16.00  97.00  98.21   58
 10  \w      2.00  27.00   0.50    0.05    --   32.00  97.00  69.41   50
 11  \w      7.00  32.00   0.50    0.05    --   36.00  94.00-154.95   50
 12  \w      6.00  31.00   0.50    0.05    --   36.00  96.00 143.75   50
 13  \w     17.00  42.00   0.50    0.05    --   44.00  91.00 -13.52   50
 14  \w    -85.00 -43.00   0.50    0.05    --  -49.62 -38.00  30.00   84
 15  \w     56.00  86.00   0.50    0.05    --   49.62  19.00-120.00   60
 16  \w     29.00  55.00   0.50    0.05    --   49.62  77.00 -60.00   52
 17  \w    -20.00  57.00   0.50    0.05    --   49.62 -38.00 -60.00  154
 18  \w     43.00 118.00   0.50    0.05    --   49.62  19.00   0.00  150
 19  \w     29.00  55.00   0.50    0.05    --   49.62  77.00 150.00   52
 20  \w     29.00  63.00   0.50    0.05    --   49.62  77.00  90.00   68
 21  \w     30.00  68.00   0.50    0.05    --   49.62  77.00 -90.00   76
 22  \w     31.00  71.00   0.50    0.05    --   52.00  80.00  41.74   80
 23  \w     37.00  63.00   0.50    0.05    --   56.00  76.00 -40.51   52
 24  \w     38.00  64.00   0.50    0.05    --   56.00  74.00 164.86   52
 25  \w     35.00  61.00   0.50    0.05    --   56.00  81.00-150.20   52
 26  \w     70.00  96.00   0.50    0.05    --   56.00  74.00 164.86   52
 27  \w    -73.00 -40.00   0.50    0.05    --  -60.00 -74.00 -10.17   66
 28  \w    -64.00 -38.00   0.50    0.05    --  -60.00 -81.00-164.72   52
 29  \w     42.00  68.00   0.50    0.05    --   60.00  74.00 -71.30   52
 30  \w     41.00  67.00   0.50    0.05    --   60.00  75.00 -29.19   52
 31  \w     42.00  67.00   0.50    0.05    --   60.00  73.00 112.85   50
 32  \w    -78.00 -49.00   0.50    0.05    --  -64.00 -68.00  35.01   58
 33  \w     44.00  73.00   0.50    0.05    --   64.00  76.00 -97.64   58
 34  \w    -76.00 -50.00   0.50    0.05    --  -68.00 -70.00 -52.43   52
 35  \w    -71.00 -45.00   0.50    0.05    --  -68.00 -83.00-167.87   52
 36  \w     48.00  73.00   0.50    0.05    --   68.00  75.00 136.82   50
 37  \w    -70.00 -45.00   0.50    0.05    --  -68.00 -83.00  29.73   50
 38  \w     52.00  78.00   0.50    0.05    --   72.00  75.00-120.74   52
 39  \w    -83.00 -57.00   0.50    0.05    --  -72.00 -67.00  -7.42   52
 40  \w    -94.00 -60.00   0.50    0.05    --  -80.00 -74.00  59.24   68
 41  \w    -83.00 -57.00   0.50    0.05    --  -80.00 -82.00  -3.18   52
 42  \w   -113.00 -63.00   0.50    0.05    --  -84.25 -77.00  60.00  100
 43  \w   -142.00-117.00   0.50    0.05    --  -84.25 -77.00  60.00   50
 44  \w    -94.00 -63.00   0.50    0.05    --  -84.25 -77.00 -30.00   62
 45  \w    -96.00 -71.00   0.50    0.05    --  -84.25 -65.00 116.91   50
 46  \w    -90.00 -64.00   0.50    0.05    --  -84.25 -77.00 -60.00   52
 47  \w   -106.00 -71.00   0.50    0.05    --  -84.25 -61.00-150.00   70
 48  \w   -155.00-130.00   0.50    0.05    --  -84.25 -77.00 -60.00   50
 49  \w    -90.00 -64.00   0.50    0.05    --  -84.25 -77.00  90.00   52
 50  \w   -147.00-121.00   0.50    0.05    --  -84.25 -77.00  90.00   52
 51  \w    -91.00 -65.00   0.50    0.05    --  -84.25 -73.00 -92.60   52
 52  \w    -96.00 -65.00   0.50    0.05    --  -84.25 -74.00-105.62   62
 53  \w    -88.00 -63.00   0.50    0.05    --  -84.25 -77.00 150.00   50
 54  \w    -89.00 -63.00   0.50    0.05    --  -84.25 -77.00-180.00   52
 55  \w    -98.00 -63.00   0.50    0.05    --  -84.25 -77.00  21.29   70
 56  \w    -97.00 -65.00   0.50    0.05    --  -84.25 -73.00  99.33   64
 57  \w    -90.00 -64.00   0.50    0.05    --  -84.25 -75.00 -78.83   52
 58  \w    -94.00 -67.00   0.50    0.05    --  -84.25 -70.00-165.95   54
 59  \w    133.00 160.00   0.50    0.05    --  105.75  68.00-132.54   54
 60  \w     90.00 119.00   0.50    0.05    --  105.75  68.00-132.54   58
 61  \w     35.00 109.00   0.50    0.05    --  105.75 -94.00  30.00  148
 62  \w     62.00 119.00   0.50    0.05    --  105.75 -61.00   0.00  114
 63  \w     60.00 109.00   0.50    0.05    --  105.75 -94.00 -60.00   98
 64  \w    133.00 169.00   0.50    0.05    --  105.75  77.00-180.00   72
 65  \w    147.00 178.00   0.50    0.05    --  105.75  77.00  90.00   62
 66  \w    145.00 177.00   0.50    0.05    --  105.75  77.00 120.00   64
 67  \w     87.00 132.00   0.50    0.05    --  105.75  77.00  90.00   90
 68  \w    141.00 167.00   0.50    0.05    --  105.75  77.00  60.00   52
 69  \w     85.00 120.00   0.50    0.05    --  105.75  77.00 120.00   70
 70  \w     86.00 125.00   0.50    0.05    --  105.75  77.00-180.00   78
 71  \w     88.00 115.00   0.50    0.05    --  105.75  77.00  60.00   54
 72  \w     86.00 144.00   0.50    0.05    --  105.75  77.00   0.00  116
 73  \w     38.00  69.00   0.50    0.05    --  105.75 -30.00-120.00   62
 74  \w    141.00 174.00   0.50    0.05    --  105.75  15.00-180.00   66
 75  \w     49.00  78.00   0.50    0.05    --  105.75-125.00-180.00   58
 76  \w     66.00 116.00   0.50    0.05    --  105.75-125.00 -90.00  100
 77  \w    129.00 169.00   0.50    0.05    --  105.75  77.00-150.00   80
 78  \w     96.00 159.00   0.50    0.05    --  105.75  61.00-120.00  126
 79  \w     85.00 119.00   0.50    0.05    --  105.75  77.00-150.00   68
 80  \w    153.00 178.00   0.50    0.05    --  105.75  77.00 150.00   50
 81  \w     85.00 119.00   0.50    0.05    --  105.75  77.00 150.00   68
 82  \w    150.00 176.00   0.50    0.05    --  105.75  77.00 -30.00   52
 83  \w     95.00 166.00   0.50    0.05    --  105.75  61.00 -90.00  142
 84  \w    122.00 176.00   0.50    0.05    --  105.75  77.00 -60.00  108
 85  \w     85.00 113.00   0.50    0.05    --  105.75  77.00 -60.00   56
 86  \w     85.00 127.00   0.50    0.05    --  105.75  77.00 -30.00   84
 87  \w     99.00 134.00   0.50    0.05    --  105.75  15.00-180.00   70
 88  \w     98.00 156.00   0.50    0.05    --  105.75  61.00 -30.00  116
 89  \w     93.00 153.00   0.50    0.05    --  105.75  61.00  60.00  120
 90  \w     78.00 117.00   0.50    0.05    --  105.75 -61.00 -90.00   78
 91  \w     35.00  95.00   0.50    0.05    --  105.75 -94.00-120.00  120
 92  \w    143.00 178.00   0.50    0.05    --  105.75  77.00-120.00   70
 93  \w     85.00 112.00   0.50    0.05    --  105.75  77.00-120.00   54
 94  \w     37.00  79.00   0.50    0.05    --  105.75 -94.00-150.00   84
 95  \w     94.00 150.00   0.50    0.05    --  105.75  61.00  30.00  112
 96  \w     93.00 178.00   0.50    0.05    --  105.75  61.00-180.00  170
 97  \w     55.00  92.00   0.50    0.05    --  105.75 -94.00 150.00   74
 98  \w     48.00 114.00   0.50    0.05    --  105.75-125.00 150.00  132
 99  \w    135.00 177.00   0.50    0.05    --  105.75  77.00  30.00   84
100  \w    142.00 167.00   0.50    0.05    --  105.75 125.00-180.00   50
101  \w     34.00 107.00   0.50    0.05    --  105.75 -94.00   0.00  146
102  \w    131.00 177.00   0.50    0.05    --  105.75  77.00 -90.00   92
103  \w    135.00 161.00   0.50    0.05    --  105.75  61.00 150.00   52
104  \w     92.00 131.00   0.50    0.05    --  105.75  61.00 150.00   78
105  \w     88.00 119.00   0.50    0.05    --  105.75  77.00 -90.00   62
106  \w     85.00 111.00   0.50    0.05    --  105.75  77.00  30.00   52
107  \w    134.00 159.00   0.50    0.05    --  105.75  61.00 -60.00   50
108  \w     93.00 122.00   0.50    0.05    --  105.75  61.00 -60.00   58
109  \w     93.00 169.00   0.50    0.05    --  105.75  61.00   0.00  152
110  \w     41.00  88.00   0.50    0.05    --  105.75 -45.00-120.00   94
111  \w     97.00 157.00   0.50    0.05    --  105.75  61.00  90.00  120
112  \w     42.00 107.00   0.50    0.05    --  105.75 -94.00-180.00  130
113  \w     91.00 116.00   0.50    0.05    --  105.75-125.00-180.00   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      0.0572657000
_diffrn_orient_matrix_UB_12      0.1009576000
_diffrn_orient_matrix_UB_13      0.0939732000
_diffrn_orient_matrix_UB_21      0.0747641000
_diffrn_orient_matrix_UB_22      0.0813221000
_diffrn_orient_matrix_UB_23      -0.0784924000
_diffrn_orient_matrix_UB_31      -0.1871273000
_diffrn_orient_matrix_UB_32      0.0261803000
_diffrn_orient_matrix_UB_33      -0.0464163000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            35534
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.830
_diffrn_reflns_theta_min         3.757
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.538
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58716
_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    1.496
_exptl_crystal_description       block
_exptl_crystal_F_000             502
_exptl_crystal_size_max          0.185
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.538
_refine_diff_density_min         -1.452
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.139
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         4592
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0316P)^2^+2.4232P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0823
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4540
_reflns_number_total             4592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01716_si_002.cif
_cod_data_source_block           2f
_cod_database_code               4034092
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         RhClC25H24N2
_shelx_estimated_absorpt_t_max   0.691
_shelx_estimated_absorpt_t_min   0.336
_reflns_odcompleteness_completeness 99.78
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C23(H23),
 C24(H24), C25(H25)
2.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)
;