Intramolecular Frustrated Lewis Pair Mediated Approach to the C=O Bond Activation and Cleavage of Carbon Dioxide
Krempner, Clemens; Manankandayalage, Chamila; Katakam, Nandakumar; Unruh, Daniel K.; Aquino, Adelia; Chemical Communications  (2022) –; doi:10.1039/D2CC03413A

data_7130384
_publ_section_title
;
 Intramolecular Frustrated Lewis Pair Mediated Approach to the C=O Bond
 Activation and Cleavage of Carbon Dioxide
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03413A
_journal_year                    2022
_chemical_formula_moiety         'C40 H60 B2 N6 O3, 2(C F3 O3 S), C H2 Cl2'
_chemical_formula_sum            'C43 H62 B2 Cl2 F6 N6 O9 S2'
_chemical_formula_weight         1077.62
_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             2021-03-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-12-10 deposited with the CCDC.	2022-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                74.5510(10)
_cell_angle_beta                 83.6470(10)
_cell_angle_gamma                75.3530(10)
_cell_formula_units_Z            2
_cell_length_a                   12.96610(10)
_cell_length_b                   13.2799(2)
_cell_length_c                   15.5932(2)
_cell_measurement_reflns_used    30378
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      77.2980
_cell_measurement_theta_min      2.9320
_cell_volume                     2501.15(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.958
_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    -83.00  -3.00   0.50    0.20    --  -47.95 112.00 171.00  160
  2  \w     25.00  89.00   0.50    0.20    --   47.95-112.00  79.00  128
  3  \w    -82.00 -13.00   0.50    0.81    --  -86.25 112.00 171.00  138
  4  \w   -159.00 -81.00   0.50    0.81    --  -86.25-112.00  79.00  156
  5  \w    103.00 178.00   0.50    0.81    --  107.74 112.00 171.00  150
  6  \w     35.00 108.00   0.50    0.81    --  107.74-112.00  79.00  146
  7  \w    -71.00  25.00   0.50    0.20    --  -47.95  77.00 -60.00  192
  8  \w   -120.00 -73.00   0.50    0.20    --  -47.95-125.00   0.00   94
  9  \w    -24.00  28.00   0.50    0.20    --  -47.95  19.00-120.00  104
 10  \w   -120.00 -73.00   0.50    0.20    --  -47.95-125.00-120.00   94
 11  \w    -86.00 -13.00   0.50    0.20    --  -47.95 125.00  90.00  146
 12  \w   -120.00 -73.00   0.50    0.20    --  -47.95-125.00 -90.00   94
 13  \w    -24.00  28.00   0.50    0.20    --  -47.95  19.00   0.00  104
 14  \w    -25.00  45.00   0.50    0.20    --   47.95 -38.00 150.00  140
 15  \w    -41.00 -13.00   0.50    0.81    --  -86.25  38.00  90.00   56
 16  \w   -159.00 -73.00   0.50    0.81    --  -86.25 -38.00 -30.00  172
 17  \w    -41.00 -13.00   0.50    0.81    --  -86.25  38.00 120.00   56
 18  \w    -41.00 -13.00   0.50    0.81    --  -86.25  38.00 -60.00   56
 19  \w    -41.00 -13.00   0.50    0.81    --  -86.25  38.00 -30.00   56
 20  \w    -41.00 -13.00   0.50    0.81    --  -86.25  38.00  30.00   56
 21  \w   -162.00 -73.00   0.50    0.81    --  -86.25 -19.00 120.00  178
 22  \w     95.00 178.00   0.50    0.81    --  107.74 125.00 -60.00  166
 23  \w     35.00  68.00   0.50    0.81    --  107.74 -57.00-120.00   66
 24  \w     35.00  68.00   0.50    0.81    --  107.74 -57.00-150.00   66
 25  \w     35.00 111.00   0.50    0.81    --  107.74-125.00  60.00  152
 26  \w     95.00 178.00   0.50    0.81    --  107.74  38.00 -90.00  166
 27  \w     35.00  68.00   0.50    0.81    --  107.74 -57.00 -90.00   66
 28  \w     35.00 111.00   0.50    0.81    --  107.74-125.00   0.00  152
 29  \w     35.00 106.00   0.50    0.81    --  107.74 -99.00 120.00  142
 30  \w     35.00 106.00   0.50    0.81    --  107.74 -99.00 150.00  142
 31  \w     95.00 178.00   0.50    0.81    --  107.74  38.00-150.00  166
 32  \w     35.00 111.00   0.50    0.81    --  107.74-125.00  30.00  152
 33  \w     35.00 106.00   0.50    0.81    --  107.74 -99.00 -90.00  142
 34  \w     35.00  68.00   0.50    0.81    --  107.74 -57.00 -30.00   66
 35  \w     35.00 111.00   0.50    0.81    --  107.74-125.00 -60.00  152
 36  \w     93.00 178.00   0.50    0.81    --  107.74  57.00  30.00  170
 37  \w     35.00 106.00   0.50    0.81    --  107.74 -99.00-150.00  142
 38  \w     95.00 149.50   0.50    0.81    --  107.74  38.00 150.00  109
;
_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      -0.0426137000
_diffrn_orient_matrix_UB_12      0.0798902000
_diffrn_orient_matrix_UB_13      0.0585774000
_diffrn_orient_matrix_UB_21      -0.0484318000
_diffrn_orient_matrix_UB_22      0.0863045000
_diffrn_orient_matrix_UB_23      -0.0819227000
_diffrn_orient_matrix_UB_31      -0.1046523000
_diffrn_orient_matrix_UB_32      -0.0385678000
_diffrn_orient_matrix_UB_33      0.0196571000
_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  0.0364
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            41852
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.464
_diffrn_reflns_theta_min         2.943
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.652
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.581
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_description       block
_exptl_crystal_F_000             1128
_exptl_crystal_recrystallization_method 'Slow evaporation from dichloromethane'
_exptl_crystal_size_max          0.182
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.359
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.00088(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.949
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     640
_refine_ls_number_reflns         10180
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.949
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0482P)^2^+1.6300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9322
_reflns_number_total             10180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03413a2.cif
_cod_data_source_block           11
_cod_database_code               7130384
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88  H124  B2  Cl4  F12  N12  O18  S4  '
_shelx_estimated_absorpt_t_max   0.738
_shelx_estimated_absorpt_t_min   0.644
_reflns_odcompleteness_completeness 99.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C15(H15), C19(H19), C34(H34), C38(H38)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B), C21(H21A,
 H21B), C22(H22A,H22B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C44(H44A,H44B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C25(H25), C26(H26), C27(H27), C28(H28)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C)
;
_shelx_res_checksum              6490
_shelx_hkl_checksum              43471
_olex2_exptl_crystal_mounting_method 'MiTeGen 50 micron MicroLoop'
_olex2_submission_original_sample_id kre21_07
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.383
_oxdiff_exptl_absorpt_empirical_full_min 0.612