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_7130383
_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
'C21 H30 B F3 N3 O4 S, C F3 O3 S, 0.5(C6 H5 Cl)'
_chemical_formula_sum            'C25 H32.5 B Cl0.5 F6 N3 O7 S2'
_chemical_formula_weight         693.69
_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             2021-03-31
_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                70.1030(10)
_cell_angle_beta                 80.3630(10)
_cell_angle_gamma                89.3920(10)
_cell_formula_units_Z            2
_cell_length_a                   8.15130(10)
_cell_length_b                   12.7879(2)
_cell_length_c                   15.9378(3)
_cell_measurement_reflns_used    28500
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      77.1860
_cell_measurement_theta_min      2.9790
_cell_volume                     1538.18(4)
_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      99.9(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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   -119.00 -35.00   0.50    1.08    --  -47.95 -46.00-100.00  168
  2  \w    -50.00  25.00   0.50    1.08    --  -47.95  46.00  48.00  150
  3  \w    -23.00  54.00   0.50    1.08    --   47.95 -46.00-100.00  154
  4  \w     35.00 119.00   0.50    1.08    --   47.95  46.00  48.00  168
  5  \w    -50.00 -14.00   0.50    4.31    --  -86.25  46.00  48.00   72
  6  \w   -159.00 -73.00   0.50    4.31    --  -86.25 -46.00-100.00  172
  7  \w     95.00 178.00   0.50    4.31    --  107.74  46.00  48.00  166
  8  \w    -20.00  18.00   0.50    1.08    --   14.00 101.00 -45.36   76
  9  \w     -1.00  31.00   0.50    1.08    --   30.00  95.00  19.59   64
 10  \w      1.00  27.00   0.50    1.08    --   34.00  98.00-152.31   52
 11  \w     11.00  43.00   0.50    1.08    --   38.00  86.00  53.06   64
 12  \w     13.00  43.00   0.50    1.08    --   42.00  90.00-105.09   60
 13  \w     12.00  39.00   0.50    1.08    --   42.00  92.00-158.78   54
 14  \w     17.00  43.00   0.50    1.08    --   46.00  90.00  73.95   52
 15  \w    -71.00  25.00   0.50    1.08    --  -47.95  77.00 150.00  192
 16  \w   -121.00 -36.00   0.50    1.08    --  -47.95 -38.00-180.00  170
 17  \w   -121.00 -36.00   0.50    1.08    --  -47.95 -38.00 -30.00  170
 18  \w   -121.00 -36.00   0.50    1.08    --  -47.95 -38.00 120.00  170
 19  \w   -120.00 -25.00   0.50    1.08    --  -47.95 -77.00 -90.00  190
 20  \w     34.00  96.00   0.50    1.08    --   47.95-125.00  60.00  124
 21  \w     25.00 120.00   0.50    1.08    --   47.95  77.00  30.00  190
 22  \w     27.00 122.00   0.50    1.08    --   50.00  77.00 135.72  190
 23  \w     32.00 126.00   0.50    1.08    --   54.00  75.00 -28.49  188
 24  \w     33.00 126.00   0.50    1.08    --   54.00  74.00-144.39  186
 25  \w     37.00 131.00   0.50    1.08    --   58.00  74.00  10.64  188
 26  \w     37.00 131.00   0.50    1.08    --   58.00  72.00 101.08  188
 27  \w     36.00 131.00   0.50    1.08    --   58.00  76.00 154.31  190
 28  \w   -135.00 -40.00   0.50    1.08    --  -62.00 -75.00 141.18  190
 29  \w     40.00  65.00   0.50    1.08    --   62.00  75.00-107.78   50
 30  \w     41.00  66.00   0.50    1.08    --   62.00  73.00 -43.79   50
 31  \w     40.00  83.00   0.50    1.08    --   62.00  76.00 120.02   86
 32  \w     40.00  67.00   0.50    1.08    --   62.00  76.00-134.48   54
 33  \w    -70.00 -45.00   0.50    1.08    --  -66.00 -73.00  44.88   50
 34  \w    -72.00 -46.00   0.50    1.08    --  -66.00 -71.00 -92.60   52
 35  \w    -73.00 -47.00   0.50    1.08    --  -66.00 -68.00 -60.49   52
 36  \w    -72.00 -46.00   0.50    1.08    --  -66.00 -71.00 122.34   52
 37  \w   -134.00-109.00   0.50    1.08    --  -66.00 -69.00 -38.16   50
 38  \w    -74.00 -47.00   0.50    1.08    --  -66.00 -69.00 -38.16   54
 39  \w    103.00 129.00   0.50    1.08    --   66.00  76.00 -97.93   52
 40  \w     44.00  69.00   0.50    1.08    --   66.00  76.00 -97.93   50
 41  \w    -77.00 -51.00   0.50    4.31    --  -70.00 -68.00 129.11   52
 42  \w    -78.00 -52.00   0.50    4.31    --  -70.00 -66.00 164.30   52
 43  \w   -139.00-113.00   0.50    4.31    --  -74.00 -68.00   5.22   52
 44  \w    -80.00 -54.00   0.50    4.31    --  -74.00 -72.00  -3.23   52
 45  \w    -81.00 -55.00   0.50    4.31    --  -74.00 -68.00   5.22   52
 46  \w    -81.00 -56.00   0.50    4.31    --  -74.00 -64.00 -73.23   50
 47  \w    -79.00 -53.00   0.50    4.31    --  -74.00 -74.00 117.41   52
 48  \w    -80.00 -54.00   0.50    4.31    --  -74.00 -70.00 -99.59   52
 49  \w    -96.00 -60.00   0.50    4.31    --  -78.00 -64.00  46.27   72
 50  \w    -87.00 -60.00   0.50    4.31    --  -78.00 -64.00-156.32   54
 51  \w     55.00  81.00   0.50    4.31    --   78.00  77.00-158.07   52
 52  \w    -80.00 -55.00   0.50    4.31    --  -78.00 -76.00  40.82   50
 53  \w    -89.00 -63.00   0.50    4.31    --  -82.00 -68.00 105.21   52
 54  \w    -90.00 -64.00   0.50    4.31    --  -82.00 -65.00-137.14   52
 55  \w    -86.00 -60.00   0.50    4.31    --  -82.00 -76.00-139.01   52
 56  \w    -93.00 -59.00   0.50    4.31    --  -82.00 -76.00 101.58   68
 57  \w    -90.00 -65.00   0.50    4.31    --  -86.25 -72.00 122.19   50
 58  \w    -40.00 -13.00   0.50    4.31    --  -86.25  38.00  90.00   54
 59  \w   -123.00 -97.00   0.50    4.31    --  -86.25 -77.00-150.00   52
 60  \w    -94.00 -66.00   0.50    4.31    --  -86.25 -70.00-118.59   56
 61  \w   -159.00-108.00   0.50    4.31    --  -86.25 -77.00  41.73  102
 62  \w    -89.00 -63.00   0.50    4.31    --  -86.25 -77.00  60.00   52
 63  \w   -100.00 -65.00   0.50    4.31    --  -86.25 -75.00 -14.07   70
 64  \w   -110.00 -63.00   0.50    4.31    --  -86.25 -77.00  90.00   94
 65  \w   -101.00 -65.00   0.50    4.31    --  -86.25 -74.00  19.85   72
 66  \w    -88.00 -63.00   0.50    4.31    --  -86.25 -77.00-180.00   50
 67  \w   -159.00-110.00   0.50    4.31    --  -86.25 -77.00-180.00   98
 68  \w    -91.00 -65.00   0.50    4.31    --  -86.25 -77.00   0.00   52
 69  \w   -102.00 -63.00   0.50    4.31    --  -86.25 -77.00 -30.00   78
 70  \w   -145.00-119.00   0.50    4.31    --  -86.25 -77.00   0.00   52
 71  \w   -104.00 -66.00   0.50    4.31    --  -86.25 -77.00 -90.00   76
 72  \w   -152.00-119.00   0.50    4.31    --  -86.25 -57.00 120.00   66
 73  \w   -138.00 -66.00   0.50    4.31    --  -86.25 -74.00-174.01  144
 74  \w    -92.00 -63.00   0.50    4.31    --  -86.25 -77.00 150.00   58
 75  \w    -92.00 -66.00   0.50    4.31    --  -86.25 -73.00   5.29   52
 76  \w    -97.00 -67.00   0.50    4.31    --  -86.25 -68.00 158.49   60
 77  \w   -154.00-128.00   0.50    4.31    --  -86.25 -77.00 150.00   52
 78  \w    -98.00 -68.00   0.50    4.31    --  -86.25 -68.00 -59.90   60
 79  \w    -63.00 -30.00   0.50    4.31    --  -86.25  57.00-150.00   66
 80  \w    -88.00 -63.00   0.50    4.31    --  -86.25 -77.00  41.73   50
 81  \w    -96.00 -66.00   0.50    4.31    --  -86.25 -72.00 -83.77   60
 82  \w    -90.00 -63.00   0.50    4.31    --  -86.25 -77.00-150.00   54
 83  \w    -90.00 -64.00   0.50    4.31    --  -86.25 -75.00 -59.93   52
 84  \w     72.00 155.00   0.50    4.31    --   90.00  69.00  43.11  166
 85  \w     97.00 178.00   0.50    4.31    --  107.74  38.00-120.00  162
 86  \w     85.00 128.00   0.50    4.31    --  107.74  77.00 120.00   86
 87  \w     70.00 106.00   0.50    4.31    --  107.74 -99.00  30.00   72
 88  \w     38.00  68.00   0.50    4.31    --  107.74 -57.00-150.00   60
 89  \w     35.00  65.00   0.50    4.31    --  107.74 -57.00  30.00   60
 90  \w     86.00 157.00   0.50    4.31    --  107.74  77.00  60.00  142
 91  \w     36.00  61.00   0.50    4.31    --  107.74 -99.00  30.00   50
 92  \w     66.00 106.00   0.50    4.31    --  107.74 -99.00-120.00   80
 93  \w     39.00  65.00   0.50    4.31    --  107.74 -99.00-120.00   52
 94  \w    102.00 168.00   0.50    4.31    --  107.74  38.00 120.00  132
 95  \w     35.00  74.00   0.50    4.31    --  107.74 -99.00 -60.00   78
 96  \w     88.00 175.00   0.50    4.31    --  107.74  77.00  30.00  174
 97  \w     96.00 178.00   0.50    4.31    --  107.74  38.00 -60.00  164
 98  \w     75.00 105.00   0.50    4.31    --  107.74 -99.00  90.00   60
 99  \w     35.00  71.00   0.50    4.31    --  107.74 -99.00  90.00   72
100  \w    106.00 176.00   0.50    4.31    --  107.74  38.00-150.00  140
101  \w     88.00 174.00   0.50    4.31    --  107.74  77.00 -90.00  172
102  \w     77.00 106.00   0.50    4.31    --  107.74 -99.00 120.00   58
103  \w     95.00 175.00   0.50    4.31    --  107.74 125.00 -30.00  160
104  \w     46.00  72.00   0.50    4.31    --  107.74 -99.00 120.00   52
105  \w     35.00 109.00   0.50    4.31    --  107.74-125.00  30.00  148
106  \w    112.00 160.00   0.50    4.31    --  107.74  77.00 150.00   96
107  \w     39.00  68.00   0.50    4.31    --  107.74 -57.00 -90.00   58
108  \w    102.00 155.00   0.50    4.31    --  107.74  38.00   0.00  106
109  \w     39.00  64.00   0.50    4.31    --  107.74 -57.00   0.00   50
110  \w    121.00 173.00   0.50    4.31    --  107.74  38.00 -30.00  104
111  \w     37.00 107.00   0.50    4.31    --  107.74 -77.00 120.00  140
112  \w     77.00 103.00   0.50    4.31    --  107.74 -99.00 -60.00   52
113  \w     35.00  65.00   0.50    4.31    --  107.74 -57.00  60.00   60
;
_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      -0.0107558000
_diffrn_orient_matrix_UB_12      -0.1260833000
_diffrn_orient_matrix_UB_13      0.0531454000
_diffrn_orient_matrix_UB_21      -0.1712932000
_diffrn_orient_matrix_UB_22      -0.0100106000
_diffrn_orient_matrix_UB_23      -0.0260945000
_diffrn_orient_matrix_UB_31      0.0859345000
_diffrn_orient_matrix_UB_32      -0.0214079000
_diffrn_orient_matrix_UB_33      -0.0859803000
_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  0.0597
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            42844
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         2.994
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.731
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.569
_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    1.498
_exptl_crystal_description       irregular
_exptl_crystal_F_000             718
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.367
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.00104(18)
_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   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         5438
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0435P)^2^+0.8547P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.1013
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4650
_reflns_number_total             5438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03413a2.cif
_cod_data_source_block           8
_cod_original_formula_sum        'C25 H32.50 B Cl0.50 F6 N3 O7 S2'
_cod_database_code               7130383
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54  H62  F12  N8  O14  S4  '
_shelx_estimated_absorpt_t_max   0.887
_shelx_estimated_absorpt_t_min   0.655
_reflns_odcompleteness_completeness 99.14
_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. Others
 Fixed Sof: Cl1(0.5) C23(0.5) C28(0.5) H28(0.5) C27(0.5) H27(0.5) C26(0.5)
 H26(0.5) C25(0.5) H25(0.5) C24(0.5) H24(0.5)
3.a Ternary CH refined with riding coordinates:
 C13(H13), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C28(H28), C27(H27), C26(H26), C25(H25),
 C24(H24)
3.d Fitted hexagon refined as free rotating group:
 C23(C28,C27,C26,C25,C24)
3.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              98536
_shelx_hkl_checksum              64405
_olex2_exptl_crystal_mounting_method 'Hampton Reserach 20 micron nylon CryoLoop'
_olex2_submission_original_sample_id kre21_10
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   6138
_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 1.871
_oxdiff_exptl_absorpt_empirical_full_min 0.476