Ortho-aryl substituted DPEphos ligands: Rhodium Complexes Featuring C‒H Anagostic Interactions and B‒H Agostic Bonds.
Race, James; Burnage, Arron; Boyd, Timothy M.; Heyam, Alex; Martinez-Martinez, Antonio J.; Macgregor, Stuart Alan; Weller, Andrew S.; Chemical Science  (2021) –; doi:10.1039/D1SC01430G

data_1562856
_publ_section_title
;
 Ortho-aryl substituted DPEphos ligands: Rhodium Complexes Featuring C--H
 Anagostic Interactions and B--H Agostic Bonds.
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01430G
_journal_year                    2021
_chemical_formula_moiety
'C43 H36 O P2 Rh, C32 H12 B F24, C5 H12, 0.5(C6 H4 F2)'
_chemical_formula_sum            'C83 H62 B F25 O P2 Rh'
_chemical_formula_weight         1725.98
_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
_audit_creation_date             2020-09-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-02-21 deposited with the CCDC.	2021-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                106.3620(10)
_cell_angle_beta                 96.9450(10)
_cell_angle_gamma                91.2350(10)
_cell_formula_units_Z            2
_cell_length_a                   13.4274(2)
_cell_length_b                   13.6083(2)
_cell_length_c                   21.8679(3)
_cell_measurement_reflns_used    37825
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      71.1150
_cell_measurement_theta_min      4.4680
_cell_volume                     3799.34(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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    -10.00  28.00   1.00    5.51    --    0.00 -77.00-120.00   38
  2  \w      7.00  40.00   1.00    5.51    --    0.00  77.00  90.00   33
  3  \w    -13.00  30.00   1.00    5.51    --    0.00 -77.00-180.00   43
  4  \w    -20.00  49.00   1.00    5.51    --    0.00  57.00  30.00   69
  5  \w      7.00  33.00   1.00   22.05    --   54.00 -99.00  30.00   26
  6  \w     56.00 103.00   1.00   22.05    --   54.00  57.00 -60.00   47
  7  \w      8.00  75.00   1.00   22.05    --   54.00 -99.00   0.00   67
  8  \w     -6.00  61.00   1.00   22.05    --   54.00 -57.00  30.00   67
  9  \w    -16.00  96.00   1.00   22.05    --   54.00 -19.00 150.00  112
 10  \w     37.00 120.00   1.00   22.05    --   54.00  57.00 150.00   83
 11  \w     64.00  96.00   1.00   22.05    --   54.00 -99.00  30.00   32
 12  \w     23.00  95.00   1.00   22.05    --   54.00 -99.00-150.00   72
 13  \w     37.00 109.00   1.00   40.00    --  108.00-111.00-180.00   72
 14  \w     39.00  65.00   1.00   40.00    --  108.00-111.00 -90.00   26
 15  \w    136.00 172.00   1.00   40.00    --  108.00  77.00  30.00   36
 16  \w    110.00 155.00   1.00   40.00    --  108.00  77.00 -90.00   45
 17  \w     64.00 109.00   1.00   40.00    --  108.00-111.00  60.00   45
 18  \w     83.00 176.00   1.00   40.00    --  108.00  25.00  60.00   93
 19  \w     38.00  79.00   1.00   40.00    --  108.00 -91.00-150.00   41
 20  \w    103.00 178.00   1.00   40.00    --  108.00  77.00 -60.00   75
 21  \w     56.00  99.00   1.00   40.00    --  108.00 -91.00  90.00   43
 22  \w     70.00 117.00   1.00   40.00    --  108.00 178.00-180.00   47
 23  \w    143.00 175.00   1.00   40.00    --  108.00  50.00   0.00   32
 24  \w    121.00 159.00   1.00   40.00    --  108.00  77.00 -30.00   38
 25  \w     88.00 122.00   1.00   40.00    --  108.00  50.00   0.00   34
 26  \w     63.00 102.00   1.00   40.00    --  108.00-111.00   0.00   39
 27  \w     60.00 129.00   1.00   40.00    --  108.00 -63.00-150.00   69
 28  \w     74.00 109.00   1.00   40.00    --  108.00-111.00 -90.00   35
 29  \w    105.00 161.00   1.00   40.00    --  108.00 111.00-120.00   56
 30  \w     38.00 130.00   1.00   40.00    --  108.00 -50.00 -60.00   92
 31  \w     86.00 128.00   1.00   40.00    --  108.00  50.00 -60.00   42
 32  \w     -9.00  21.00   1.00    5.51    --    0.00 -37.00 -30.00   30
 33  \w    -24.00  42.00   1.00    5.51    --    0.00  37.00   0.00   66
 34  \w    -30.00  36.00   1.00    5.51    --    0.00  77.00 -60.00   66
 35  \w    -71.00 -12.00   1.00    5.51    --    0.00 -37.00 -30.00   59
 36  \w    -22.00   3.00   1.00    5.51    --   20.00  99.00 125.31   25
 37  \w    -47.00 -20.00   1.00   22.05    --   28.00 153.00  53.09   27
 38  \w      4.00  29.00   1.00   22.05    --   40.00  88.00 108.07   25
 39  \w      4.00  29.00   1.00   22.05    --   40.00  88.00 -75.33   25
 40  \w     16.00  41.00   1.00   22.05    --   48.00  80.00 167.59   25
 41  \w     16.00  41.00   1.00   22.05    --   48.00  80.00  44.37   25
 42  \w     16.00  41.00   1.00   22.05    --   48.00  81.00 118.62   25
 43  \w     15.00  40.00   1.00   22.05    --   48.00  82.00-154.81   25
 44  \w     16.00  42.00   1.00   22.05    --   48.00  80.00-101.85   26
 45  \w     16.00  41.00   1.00   22.05    --   48.00  81.00  13.62   25
 46  \w     15.00  40.00   1.00   22.05    --   48.00  82.00  74.26   25
 47  \w     16.00  41.00   1.00   22.05    --   48.00  81.00 -21.07   25
 48  \w     -7.00  75.00   1.00   22.05    --   54.00 -57.00  90.00   82
 49  \w     28.00  56.00   1.00   22.05    --   56.00  73.00 154.71   28
 50  \w     28.00  54.00   1.00   22.05    --   56.00  74.00-108.51   26
 51  \w     32.00  59.00   1.00   22.05    --   60.00  73.00  40.65   27
 52  \w     34.00  60.00   1.00   22.05    --   60.00  72.00-172.87   26
 53  \w     33.00  58.00   1.00   22.05    --   60.00  74.00  77.06   25
 54  \w     37.00  64.00   1.00   22.05    --   64.00  71.00 -75.61   27
 55  \w     36.00  61.00   1.00   22.05    --   64.00  74.00  -8.62   25
 56  \w     36.00  62.00   1.00   22.05    --   64.00  73.00 -62.49   26
 57  \w     37.00  64.00   1.00   22.05    --   64.00  72.00-161.88   27
 58  \w     37.00  65.00   1.00   22.05    --   64.00  73.00  21.75   28
 59  \w     36.00  62.00   1.00   22.05    --   64.00  74.00 112.62   26
 60  \w    100.00 126.00   1.00   22.05    --   68.00  74.00 140.36   26
 61  \w     40.00  67.00   1.00   22.05    --   68.00  74.00 140.36   27
 62  \w    107.00 133.00   1.00   22.05    --   68.00  70.00  59.97   26
 63  \w     40.00  91.00   1.00   22.05    --   68.00  74.00-140.72   51
 64  \w     42.00  68.00   1.00   22.05    --   68.00  70.00  59.97   26
 65  \w     41.00  68.00   1.00   22.05    --   68.00  72.00 -48.35   27
 66  \w    117.00 142.00   1.00   22.05    --   72.00  74.00  85.63   25
 67  \w     44.00  70.00   1.00   22.05    --   72.00  74.00  85.63   26
 68  \w     44.00  73.00   1.00   22.05    --   72.00  73.00-123.49   29
 69  \w     49.00  93.00   1.00   22.05    --   76.00  71.00 -20.24   44
 70  \w     49.00  79.00   1.00   22.05    --   76.00  74.00  13.36   30
 71  \w     54.00  80.00   1.00   22.05    --   76.00  64.00  59.51   26
 72  \w     48.00  97.00   1.00   22.05    --   76.00  73.00  -4.37   49
 73  \w     48.00  84.00   1.00   22.05    --   76.00  74.00-107.62   36
 74  \w     53.00  80.00   1.00   22.05    --   76.00  64.00 -33.99   27
 75  \w     54.00  81.00   1.00   22.05    --   80.00  73.00 165.56   27
 76  \w     53.00 108.00   1.00   22.05    --   80.00  71.00-157.57   55
 77  \w     54.00  80.00   1.00   22.05    --   80.00  70.00 149.60   26
 78  \w     55.00  81.00   1.00   22.05    --   80.00  69.00 -66.36   26
 79  \w     56.00  83.00   1.00   40.00    --   84.00  74.00 116.77   27
 80  \w    100.00 151.00   1.00   40.00    --   84.00  73.00  88.41   51
 81  \w     56.00  82.00   1.00   40.00    --   84.00  73.00  88.41   26
 82  \w     57.00  84.00   1.00   40.00    --   84.00  73.00  11.04   27
 83  \w     56.00  82.00   1.00   40.00    --   84.00  74.00 153.65   26
 84  \w     57.00  83.00   1.00   40.00    --   84.00  74.00-133.62   26
 85  \w     60.00 112.00   1.00   40.00    --   88.00  74.00 178.46   52
 86  \w     62.00  88.00   1.00   40.00    --   88.00  70.00 105.65   26
 87  \w     66.00 105.00   1.00   40.00    --   88.00  62.00 -90.90   39
 88  \w     65.00  90.00   1.00   40.00    --   88.00  64.00 -55.81   25
 89  \w     67.00  93.00   1.00   40.00    --   92.00  69.00  34.08   26
 90  \w     64.00  90.00   1.00   40.00    --   92.00  74.00 151.89   26
 91  \w     64.00 107.00   1.00   40.00    --   92.00  74.00 -59.21   43
 92  \w     75.00 104.00   1.00   40.00    --   96.00  57.00 102.69   29
 93  \w     68.00  94.00   1.00   40.00    --   96.00  74.00  38.75   26
 94  \w     71.00 101.00   1.00   40.00    --   96.00  70.00 -92.06   30
 95  \w     68.00 110.00   1.00   40.00    --   96.00  74.00-134.25   42
 96  \w     68.00 107.00   1.00   40.00    --   96.00  73.00 -32.98   39
 97  \w     72.00  98.00   1.00   40.00    --  100.00  74.00 158.92   26
 98  \w     72.00 104.00   1.00   40.00    --  100.00  73.00 -18.11   32
 99  \w    120.00 147.00   1.00   40.00    --  108.00  63.00 120.00   27
100  \w     86.00 112.00   1.00   40.00    --  108.00  63.00 120.00   26
101  \w    118.00 170.00   1.00   40.00    --  108.00  63.00-180.00   52
102  \w     86.00 115.00   1.00   40.00    --  108.00  63.00-180.00   29
103  \w    118.00 176.00   1.00   40.00    --  108.00  63.00  90.00   58
104  \w     87.00 113.00   1.00   40.00    --  108.00  63.00  90.00   26
105  \w     84.00 133.00   1.00   40.00    --  108.00  69.00-116.27   49
106  \w    148.00 174.00   1.00   40.00    --  108.00  69.00  56.84   26
107  \w     83.00 109.00   1.00   40.00    --  108.00  69.00  56.84   26
108  \w     87.00 124.00   1.00   40.00    --  108.00  63.00-120.00   37
109  \w     86.00 157.00   1.00   40.00    --  108.00  63.00-150.00   71
110  \w     86.00 113.00   1.00   40.00    --  108.00  50.00-150.00   27
111  \w     87.00 115.00   1.00   40.00    --  108.00  63.00 -60.00   28
112  \w     86.00 176.00   1.00   40.00    --  108.00  50.00 150.00   90
113  \w     88.00 115.00   1.00   40.00    --  108.00  63.00   0.00   27
114  \w     87.00 112.00   1.00   40.00    --  108.00  50.00 120.00   25
115  \w     88.00 119.00   1.00   40.00    --  108.00  63.00 -90.00   31
116  \w     86.00 113.00   1.00   40.00    --  108.00  50.00  30.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            76451
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.234
_diffrn_reflns_theta_min         3.391
_exptl_absorpt_coefficient_mu    3.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69668
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.81a (Rigaku Oxford Diffraction, 2020)
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    1.509
_exptl_crystal_description       plate
_exptl_crystal_F_000             1746
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.306
_refine_diff_density_min         -0.883
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1193
_refine_ls_number_reflns         14513
_refine_ls_number_restraints     406
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0428
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0658P)^2^+5.6738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1162
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13650
_reflns_number_total             14513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01430g3.cif
_cod_data_source_block           2-H
_cod_database_code               1562856
_publcif_datablock.id            {39b0f53f-91fb-4cd8-8c62-c882b5346b9e}
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.742
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C86B-C85B = C86B-C81B = C85B-C84B
 1.39 with sigma of 0.02
 C86B-F26B = C85B-F25B
 1.35 with sigma of 0.02
 C84B-C83B = C83B-C82B = C82B-C81B
 1.4 with sigma of 0.02
 C86A-C85A = C86A-C81A = C85A-C84A
 1.39 with sigma of 0.02
 C86A-F25A = C85A-F26A
 1.35 with sigma of 0.02
 C84A-C83A = C83A-C82A = C82A-C81A
 1.4 with sigma of 0.02
 C86B-C82B = C85B-C83B
 2.4 with sigma of 0.04
 C86B-C84B = C84B-C82B = C83B-C81B
 2.42 with sigma of 0.04
 C86A-F26A
 2.37 with sigma of 0.04
 C86B-F25B
 2.37 with sigma of 0.04
 C86A-C84A = C84A-C82A = C83A-C81A
 2.42 with sigma of 0.04
 C86A-C82A = C85A-C83A
 2.4 with sigma of 0.04
 C83A-C81A \\sim C84A-C82A \\sim C85A-C83A \\sim C86A-C84A \\sim C85A-C81A
\\sim C86A-C82A
 with sigma of 0.04
 C86B-F26B \\sim C85B-F25B
 with sigma of 0.02
 C86B-C81B \\sim C82B-C81B \\sim C86B-C85B \\sim C83B-C82B \\sim C84B-C83B
\\sim C85B-C84B
 with sigma of 0.02
 C86B-F25B \\sim C84B-F25B \\sim C85B-F26B \\sim C81B-F26B
 with sigma of 0.04
 C83B-C81B \\sim C84B-C82B \\sim C85B-C83B \\sim C86B-C84B \\sim C85B-C81B
\\sim C86B-C82B
 with sigma of 0.04
 C86A-F25A \\sim C85A-F26A
 with sigma of 0.02
 C86A-C81A \\sim C82A-C81A \\sim C86A-C85A \\sim C83A-C82A \\sim C84A-C83A
\\sim C85A-C84A
 with sigma of 0.02
 C86A-F26A \\sim C84A-F26A \\sim C85A-F25A \\sim C81A-F25A
 with sigma of 0.04
3. Restrained planarity
 C86B, C85B, C84B, C83B, C82B, C81B, F26B, F25B
 with sigma of 0.1
 C86A, C85A, C84A, C83A, C82A, C81A, F25A, F26A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C86B \\sim C85B \\sim C84B \\sim C83B \\sim C82B \\sim C81B \\sim F26B \\sim
F25B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
C86A \\sim C85A \\sim C84A \\sim C83A \\sim C82A \\sim C81A \\sim F25A \\sim
F26A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
Uanis(F15) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(C58)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F22A) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(F24A) \\sim Ueq, Uanis(F23A)
\\sim Ueq, Uanis(F23B) \\sim Ueq, Uanis(F24B) \\sim Ueq, Uanis(F22B) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C50) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C86B, C85B, C84B, C83B, C82B, C81B, F26B, F25B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C86A, C85A, C84A, C83A, C82A, C81A, F25A, F26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C74B)=Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(1)
 Sof(F20A)=Sof(F21A)=Sof(F19A)=Sof(C74A)=FVAR(1)
 Sof(F23B)=Sof(F24B)=Sof(F22B)=1-FVAR(2)
 Sof(F22A)=Sof(F24A)=Sof(F23A)=FVAR(2)
 Fixed Sof: C86B(0.25) C85B(0.25) C84B(0.25) H84B(0.25) C83B(0.25) H83B(0.25)
 C82B(0.25) H82B(0.25) C81B(0.25) H81B(0.25) F26B(0.25) F25B(0.25) C86A(0.25)
 C85A(0.25) C84A(0.25) H84A(0.25) C83A(0.25) H83A(0.25) C82A(0.25) H82A(0.25)
 C81A(0.25) H81A(0.25) F25A(0.25) F26A(0.25)
7.a Ternary CH refined with riding coordinates:
 C38(H38), C37(H37), C42(H42), C41(H41), C39(H39), C40(H40)
7.b Secondary CH2 refined with riding coordinates:
 C43(H43a,H43b), C79(H79a,H79b), C77(H77a,H77b), C78(H78a,H78b)
7.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C69(H69), C64(H64), C59(H59), C53(H53), C45(H45), C51(H51), C67(H67),
 C26(H26), C72(H72), C61(H61), C17(H17), C4(H4), C1(H1), C23(H23), C8(H8),
 C2(H2), C27(H27), C20(H20), C48(H48), C12(H12), C75(H75), C30(H30), C14(H14),
 C36(H36), C21(H21), C3(H3), C9(H9), C15(H15), C10(H10), C56(H56), C16(H16),
 C32(H32), C22(H22), C35(H35), C11(H11), C28(H28), C34(H34), C29(H29), C33(H33),
  C84B(H84B), C83B(H83B), C82B(H82B), C81B(H81B), C84A(H84A), C83A(H83A),
 C82A(H82A), C81A(H81A)
7.d Idealised Me refined as rotating group:
 C80(H80a,H80b,H80c), C76(H76a,H76b,H76c)
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_shelx_res_checksum              40141
_shelx_hkl_checksum              76066
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
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Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
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_publcif_funding_html
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