Reversible dehydrogenation of a primary aryl borane.
MacNeil, Connor S.; Hsiang, Shou-Jen; Hayes, Paul G.; Chemical communications (Cambridge, England) 56 (2020) 12323–12326; doi:10.1039/d0cc05503d

data_7127201
_publ_section_title
;
 Reversible dehydrogenation of a primary aryl borane.
;
_journal_issue                   82
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              12323
_journal_page_last               12326
_journal_paper_doi               10.1039/d0cc05503d
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         '2(C22 H31.5 B0.5 N1.5 O0.5 P Rh0.5)'
_chemical_formula_sum            'C44 H63 B N3 O P2 Rh'
_chemical_formula_weight         825.63
_chemical_name_systematic        1-BMes
_chemical_properties_physical    Moisture-sensitive
_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
_audit_creation_date             2020-02-11
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-02-20 deposited with the CCDC.	2020-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                65.627(2)
_cell_angle_beta                 88.777(2)
_cell_angle_gamma                77.349(2)
_cell_formula_units_Z            4
_cell_length_a                   14.5167(3)
_cell_length_b                   18.5067(4)
_cell_length_c                   19.7008(6)
_cell_measurement_reflns_used    37909
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.6990
_cell_measurement_theta_min      3.6230
_cell_volume                     4689.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.960
_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    -42.00  28.00   0.50    1.51    --  -38.50  38.00 150.00  140
  2  \w    -87.00  -6.00   0.50    1.51    --  -38.50 125.00-120.00  162
  3  \w   -108.00 -33.00   0.50    1.51    --  -38.50 -19.00 150.00  150
  4  \w     41.00 116.00   0.50    1.51    --   47.06  19.00 -30.00  150
  5  \w    -19.00  51.00   0.50    1.51    --   47.06 -38.00   0.00  140
  6  \w     35.00 105.00   0.50    6.05    --  100.13 -45.00 -30.00  140
  7  \w     97.00 169.00   0.50    6.05    --  100.13  30.00   0.00  144
  8  \w     30.00 109.00   0.50    6.05    --  100.13-111.00 -60.00  158
  9  \w     31.00 106.00   0.50    6.05    --  100.13 -95.00 150.00  150
 10  \w     32.00 104.00   0.50    6.05    --  100.13 -30.00 120.00  144
 11  \w     35.00 105.00   0.50    6.05    --  100.13 -45.00 150.00  140
 12  \w     92.00 169.00   0.50    6.05    --  100.13  15.00 -90.00  154
 13  \w     30.00 109.00   0.50    6.05    --  100.13-111.00 150.00  158
 14  \w     31.00 106.00   0.50    6.05    --  100.13 -95.00 -60.00  150
 15  \w     37.00 113.00   0.50    6.05    --  100.13 -61.00   0.00  152
 16  \w     97.00 169.00   0.50    6.05    --  100.13  30.00 -60.00  144
 17  \w     37.00 113.00   0.50    6.05    --  100.13 -61.00 -90.00  152
 18  \w     31.00 108.00   0.50    6.05    --  100.13 -15.00 -30.00  154
 19  \w     97.00 169.00   0.50    6.05    --  100.13  30.00 -30.00  144
 20  \w   -102.00 -27.00   0.50    1.51    --  -38.50 -57.00  90.00  150
 21  \w     35.00 110.00   0.50    1.51    --   47.06  57.00 120.00  150
 22  \w     35.00 110.00   0.50    1.51    --   47.06  57.00  30.00  150
 23  \w     35.00 110.00   0.50    1.51    --   47.06  57.00-150.00  150
 24  \w     87.00 163.00   0.50    6.05    --  100.13  61.00-150.00  152
 25  \w     97.00 168.00   0.50    6.05    --  100.13  33.00  56.00  142
 26  \w     92.00 169.00   0.50    6.05    --  100.13  15.00-180.00  154
 27  \w     87.00 163.00   0.50    6.05    --  100.13  61.00 120.00  152
 28  \w     97.00 169.00   0.50    6.05    --  100.13  30.00 120.00  144
 29  \w     87.00 163.00   0.50    6.05    --  100.13  61.00   0.00  152
 30  \w     97.00 169.00   0.50    6.05    --  100.13  30.00-150.00  144
 31  \w     87.00 163.00   0.50    6.05    --  100.13  61.00 150.00  152
 32  \w     87.00 163.00   0.50    6.05    --  100.13  61.00 -60.00  152
 33  \w     87.00 163.00   0.50    6.05    --  100.13  61.00-120.00  152
 34  \w     87.00 163.00   0.50    6.05    --  100.13  61.00  30.00  152
 35  \w     97.00 169.00   0.50    6.05    --  100.13  30.00  90.00  144
 36  \w     35.00 110.00   0.50    1.51    --   47.06  57.00 -30.00  150
 37  \w     35.00 110.00   0.50    1.51    --   47.06  57.00  60.00  150
 38  \w     35.00 110.00   0.50    1.51    --   47.06  57.00-180.00  150
 39  \w     35.00 110.00   0.50    1.51    --   47.06  57.00 -90.00  150
 40  \w     87.00 155.00   0.50    6.05    --  100.13  61.00 -90.00  136
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0922484000
_diffrn_orient_matrix_UB_12      -0.0222110000
_diffrn_orient_matrix_UB_13      0.0332793000
_diffrn_orient_matrix_UB_21      -0.0410382000
_diffrn_orient_matrix_UB_22      0.0894756000
_diffrn_orient_matrix_UB_23      -0.0138463000
_diffrn_orient_matrix_UB_31      -0.0413225000
_diffrn_orient_matrix_UB_32      0.0179615000
_diffrn_orient_matrix_UB_33      -0.0782018000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            87210
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.219
_diffrn_reflns_theta_min         2.791
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.831
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51688
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       needle
_exptl_crystal_F_000             1744
_exptl_crystal_preparation       'see SI'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         4.145
_refine_diff_density_min         -1.741
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     967
_refine_ls_number_reflns         18596
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0759
_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^)+(0.1075P)^2^+31.6491P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2061
_refine_ls_wR_factor_ref         0.2131
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16301
_reflns_number_total             18596
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05503d2.cif
_cod_data_source_block           ph20004
_cod_depositor_comments
'Adding full bibliography for 7127200--7127201.cif.'
_cod_database_code               7127201
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C44 H55 B1 N3 O1 P2 Rh1'
_shelx_estimated_absorpt_t_max   0.749
_shelx_estimated_absorpt_t_min   0.393
_reflns_odcompleteness_completeness 99.20
_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 C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C68(H68), C7(H7), C65(H65), C10(H10), C14(H14), C53(H53), C50(H50), C77(H77),
 C25(H25), C35(H35), C17(H17), C62(H62)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C48(H48), C23(H23), C4(H4), C24(H24), C5(H5), C21(H21), C76(H76),
 C75(H75), C47(H47), C72(H72), C73(H73), C41(H41), C57(H57), C33(H33), C58(H58),
  C82(H82), C32(H32), C60(H60), C39(H39), C61(H61), C30(H30), C84(H84), C29(H29)
2.c Idealised Me refined as rotating group:
 C67(H67A,H67B,H67C), C43(H43A,H43B,H43C), C66(H66A,H66B,H66C), C86(H86A,H86B,
 H86C), C44(H44A,H44B,H44C), C54(H54A,H54B,H54C), C70(H70A,H70B,H70C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C27(H27A,H27B,H27C), C69(H69A,H69B,H69C), C52(H52A,
 H52B,H52C), C36(H36A,H36B,H36C), C87(H87A,H87B,H87C), C13(H13A,H13B,H13C),
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C55(H55A,H55B,H55C), C15(H15A,H15B,
 H15C), C18(H18A,H18B,H18C), C51(H51A,H51B,H51C), C16(H16A,H16B,H16C), C79(H79A,
 H79B,H79C), C78(H78A,H78B,H78C), C88(H88A,H88B,H88C), C26(H26A,H26B,H26C),
 C45(H45A,H45B,H45C), C64(H64A,H64B,H64C), C63(H63A,H63B,H63C), C34(H34A,H34B,
 H34C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              61921
_shelx_fab_checksum              2428
_olex2_exptl_crystal_mounting_method 'MiTiGen loop'
_olex2_submission_original_sample_id PH20004
_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 1.936
_oxdiff_exptl_absorpt_empirical_full_min 0.527