Electrophilic and Nucleophilic Displacement Reactions at the Bridgehead Borons of Tris(pyridyl)borate Scorpionate Complexes
Goura, Joydeb; McQuade, James; Shimoyama, Daisuke; Lalancette, Roger A.; Sheridan, John B.; Jaekle, Frieder; Chemical Communications  (2022) –; doi:10.1039/D1CC06181J

data_7129474
_publ_section_title
;
 Electrophilic and Nucleophilic Displacement Reactions at the Bridgehead
 Borons of Tris(pyridyl)borate Scorpionate Complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06181J
_journal_year                    2022
_chemical_formula_moiety         'C40 H32 B2 Br2 N8 Ru, 2(C F3 O3 S), 2(H2 O)'
_chemical_formula_sum            'C42 H36 B2 Br2 F6 N8 O8 Ru S2'
_chemical_formula_weight         1241.42
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-10-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-10-25 deposited with the CCDC.	2021-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                101.3585(17)
_cell_angle_beta                 107.3380(16)
_cell_angle_gamma                98.0218(16)
_cell_formula_units_Z            1
_cell_length_a                   8.95350(15)
_cell_length_b                   9.4650(2)
_cell_length_c                   14.7807(3)
_cell_measurement_reflns_used    23834
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      76.2630
_cell_measurement_theta_min      4.8410
_cell_volume                     1145.66(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3-ac4 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.936
_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   -118.00 -58.00   0.50    0.13    --  -45.84-147.00  75.00  120
  2  \w   -102.00 -24.00   0.50    0.13    --  -45.84 147.00 124.00  156
  3  \w    -85.00 -13.00   0.50    0.13    --  -45.84 125.00 -41.00  144
  4  \w     46.00 107.00   0.50    0.13    --   45.84-147.00  75.00  122
  5  \w     34.00  95.00   0.50    0.13    --   45.84-125.00-119.00  122
  6  \w   -102.00 -24.00   0.50    0.52    --  -91.75 147.00 124.00  156
  7  \w   -152.00 -58.00   0.50    0.52    --  -91.75-147.00  75.00  188
  8  \w   -164.00 -73.00   0.50    0.52    --  -91.75-125.00-119.00  182
  9  \w     95.00 178.00   0.50    0.52    --  106.22 125.00 -41.00  166
 10  \w     80.00 167.00   0.50    0.52    --  106.22 147.00 124.00  174
 11  \w     34.00 112.00   0.50    0.52    --  106.22-125.00-119.00  156
 12  \w     46.00 127.00   0.50    0.52    --  106.22-147.00  75.00  162
 13  \w    -23.00   3.00   0.50    0.13    --   14.00 104.00 175.91   52
 14  \w    -32.00  -5.00   0.50    0.13    --  -26.00 -71.00 116.19   54
 15  \w    -32.00  -5.00   0.50    0.13    --  -26.00 -71.00 155.25   54
 16  \w      4.00  31.00   0.50    0.13    --   26.00  72.00 -27.11   54
 17  \w    -36.00 -10.00   0.50    0.13    --  -30.00 -68.00  11.17   52
 18  \w     11.00  39.00   0.50    0.13    --   30.00  66.00  26.34   56
 19  \w     16.00  44.00   0.50    0.13    --   34.00  63.00  98.03   56
 20  \w     16.00  42.00   0.50    0.13    --   34.00  64.00 158.47   52
 21  \w    -46.00 -20.00   0.50    0.13    --  -38.00 -62.00 -81.02   52
 22  \w     21.00  50.00   0.50    0.13    --   38.00  60.00-120.38   58
 23  \w     30.00 118.00   0.50    0.13    --   45.84  55.00 -26.42  176
 24  \w   -126.00 -38.00   0.50    0.13    --  -54.00 -57.00 143.30  176
 25  \w   -126.00 -38.00   0.50    0.13    --  -54.00 -57.00-121.56  176
 26  \w   -126.00 -38.00   0.50    0.13    --  -54.00 -57.00 -22.50  176
 27  \w   -126.00 -38.00   0.50    0.13    --  -54.00 -55.00   8.30  176
 28  \w   -126.00 -38.00   0.50    0.13    --  -54.00 -55.00  76.76  176
 29  \w     38.00 126.00   0.50    0.13    --   54.00  57.00 126.04  176
 30  \w     38.00 126.00   0.50    0.13    --   54.00  57.00 -87.54  176
 31  \w   -131.00 -42.00   0.50    0.13    --  -58.00 -55.00 -61.60  178
 32  \w   -135.00 -46.00   0.50    0.13    --  -62.00 -53.00-175.09  178
 33  \w   -139.00 -50.00   0.50    0.13    --  -66.00 -51.00  -2.21  178
 34  \w   -143.00 -55.00   0.50    0.52    --  -70.00 -50.00 139.99  176
 35  \w   -143.00 -55.00   0.50    0.52    --  -70.00 -48.00  38.31  176
 36  \w   -143.00 -53.00   0.50    0.52    --  -70.00 -54.00 119.46  180
 37  \w   -146.00 -58.00   0.50    0.52    --  -74.00 -51.00 -74.04  176
 38  \w   -146.00 -59.00   0.50    0.52    --  -74.00 -49.00 -30.04  174
 39  \w   -146.00 -58.00   0.50    0.52    --  -74.00 -56.00-174.23  176
 40  \w   -146.00 -58.00   0.50    0.52    --  -74.00 -55.00-102.83  176
 41  \w   -151.00 -62.00   0.50    0.52    --  -78.00 -56.00 -41.41  178
 42  \w   -151.00 -62.00   0.50    0.52    --  -78.00 -55.00 100.04  178
 43  \w   -151.00 -62.00   0.50    0.52    --  -78.00 -56.00-140.09  178
 44  \w   -151.00 -62.00   0.50    0.52    --  -78.00 -56.00  49.37  178
 45  \w   -102.00 -74.00   0.50    0.52    --  -90.00 -55.00 -85.64   56
 46  \w   -161.00-131.00   0.50    0.52    --  -90.00 -55.00 -85.64   60
 47  \w   -152.00-126.00   0.50    0.52    --  -91.75 -56.00  78.95   52
 48  \w   -102.00 -76.00   0.50    0.52    --  -91.75 -53.00-136.53   52
 49  \w   -103.00 -76.00   0.50    0.52    --  -91.75 -52.00 -96.30   54
 50  \w   -164.00 -80.00   0.50    0.52    --  -91.75 -56.00  18.06  168
 51  \w   -159.00-132.00   0.50    0.52    --  -91.75 -52.00 -96.30   54
 52  \w   -102.00 -76.00   0.50    0.52    --  -91.75 -52.00 131.59   52
 53  \w   -101.00 -76.00   0.50    0.52    --  -91.75 -53.00-170.98   50
 54  \w    -46.00 -19.00   0.50    0.52    --  -91.75  45.00  60.00   54
 55  \w   -163.00-108.00   0.50    0.52    --  -91.75 -53.00-170.98  110
 56  \w   -164.00 -77.00   0.50    0.52    --  -91.75 -55.00 -64.94  174
 57  \w   -109.00 -76.00   0.50    0.52    --  -91.75 -56.00 159.95   66
 58  \w   -164.00-126.00   0.50    0.52    --  -91.75 -52.00 131.59   76
 59  \w    -53.00 -19.00   0.50    0.52    --  -91.75  61.00  60.00   68
 60  \w   -162.00-131.00   0.50    0.52    --  -91.75 -56.00 159.95   62
 61  \w   -102.00 -76.00   0.50    0.52    --  -91.75 -53.00  24.03   52
 62  \w   -108.00 -77.00   0.50    0.52    --  -91.75 -56.00  99.59   62
 63  \w   -107.00 -76.00   0.50    0.52    --  -91.75 -56.00-117.08   62
 64  \w   -102.00 -76.00   0.50    0.52    --  -91.75 -55.00 178.86   52
 65  \w   -157.00-110.00   0.50    0.52    --  -91.75 -54.00 -52.28   94
 66  \w   -102.00 -75.00   0.50    0.52    --  -91.75 -54.00 -52.28   54
 67  \w   -163.00-124.00   0.50    0.52    --  -91.75 -56.00  99.59   78
 68  \w   -161.00-105.00   0.50    0.52    --  -91.75 -55.00 178.86  112
 69  \w   -106.00 -76.00   0.50    0.52    --  -91.75 -53.00-150.00   60
 70  \w   -110.00 -77.00   0.50    0.52    --  -91.75 -56.00 -12.26   66
 71  \w   -163.00 -76.00   0.50    0.52    --  -91.75 -56.00  61.76  174
 72  \w   -111.00 -78.00   0.50    0.52    --  -91.75 -55.00 -33.83   66
 73  \w   -107.00 -80.00   0.50    0.52    --  -91.75 -45.00-120.00   54
 74  \w   -161.00-135.00   0.50    0.52    --  -91.75 -56.00 -12.26   52
 75  \w   -163.00-133.00   0.50    0.52    --  -91.75 -45.00-120.00   60
 76  \w   -108.00 -76.00   0.50    0.52    --  -91.75 -56.00  78.95   64
 77  \w   -108.00 -76.00   0.50    0.52    --  -91.75 -53.00  44.23   64
 78  \w   -162.00-130.00   0.50    0.52    --  -91.75 -53.00  44.23   64
 79  \w   -140.00 -76.00   0.50    0.52    --  -91.75 -53.00 121.09  128
 80  \w     74.00 105.00   0.50    0.52    --  106.22 -95.00 150.00   62
 81  \w     65.00 100.00   0.50    0.52    --  106.22 -95.00-120.00   70
 82  \w     67.00  94.00   0.50    0.52    --  106.22 -77.00-120.00   54
 83  \w     35.00  60.00   0.50    0.52    --  106.22 -95.00-120.00   50
 84  \w     34.00  59.00   0.50    0.52    --  106.22 -77.00-120.00   50
 85  \w     35.00 100.00   0.50    0.52    --  106.22-125.00-180.00  130
 86  \w     44.00 100.00   0.50    0.52    --  106.22 -95.00  90.00  112
 87  \w     34.00  61.00   0.50    0.52    --  106.22 -45.00  90.00   54
 88  \w     34.00  77.00   0.50    0.52    --  106.22 -61.00  60.00   86
 89  \w     30.00  56.00   0.50    0.52    --  106.22 -15.00-150.00   52
 90  \w     34.00  61.00   0.50    0.52    --  106.22 -45.00-120.00   54
 91  \w     72.00 111.00   0.50    0.52    --  106.22-125.00  60.00   78
 92  \w     91.00 146.00   0.50    0.52    --  106.22  61.00 -30.00  110
 93  \w     35.00 105.00   0.50    0.52    --  106.22 -95.00-180.00  140
 94  \w     34.00  84.00   0.50    0.52    --  106.22 -77.00 -60.00  100
 95  \w     41.00  76.00   0.50    0.52    --  106.22 -61.00 -60.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1564639000
_diffrn_orient_matrix_UB_12      0.0221778000
_diffrn_orient_matrix_UB_13      0.0187182000
_diffrn_orient_matrix_UB_21      -0.0855968000
_diffrn_orient_matrix_UB_22      -0.0267600000
_diffrn_orient_matrix_UB_23      -0.1109341000
_diffrn_orient_matrix_UB_31      -0.0470064000
_diffrn_orient_matrix_UB_32      -0.1662773000
_diffrn_orient_matrix_UB_33      -0.0087418000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            37857
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.326
_diffrn_reflns_theta_min         4.876
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.435
_exptl_absorpt_correction_T_max  0.891
_exptl_absorpt_correction_T_min  0.663
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.799
_exptl_crystal_description       block
_exptl_crystal_F_000             618
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and acetonitrile'
_exptl_crystal_size_max          0.098
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.052
_refine_diff_density_max         3.361
_refine_diff_density_min         -1.965
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         4496
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0510
_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^)+(0.0709P)^2^+3.9972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1336
_refine_ls_wR_factor_ref         0.1365
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4146
_reflns_number_total             4496
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06181j2.cif
_cod_data_source_block           210927ral_jmcq_157_100k
_cod_original_cell_volume        1145.65(4)
_cod_database_code               7129474
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C42H32B2Br2F6N8O6RuS2
_chemical_oxdiff_usercomment     DCM/ACETONITRILE
_shelx_estimated_absorpt_t_max   0.731
_shelx_estimated_absorpt_t_min   0.571
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 O4-H4B = O4-H4A
 0.84 with sigma of 0.001
3.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C13(H13), C4(H4), C10(H10), C20(H20), C2(H2), C9(H9), C12(H12),
 C14(H14), C7(H7), C19(H19), C18(H18), C15(H15), C3(H3), C8(H8), C5(H5)
;
_shelx_res_checksum              92556
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.892
_oxdiff_exptl_absorpt_empirical_full_min 0.675