Transformation of CO<sub>2</sub> and isocyanates mediated by <i>N</i>-borane-substituted cyclic phosphine imides (BCPIs) <i>via</i> λ<sup>5</sup>-oxazaphosphetanes.
Nagai, Shun; Ogoshi, Sensuke; Hoshimoto, Yoichi; Organic & biomolecular chemistry 23 (2024) 202–206; doi:10.1039/d4ob01565g

data_7160230
_publ_section_title
;
 Transformation of CO<sub>2</sub> and isocyanates mediated by
 <i>N</i>-borane-substituted cyclic phosphine imides (BCPIs) <i>via</i>
 &#x3bb;<sup>5</sup>-oxazaphosphetanes.
;
_journal_issue                   1
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              202
_journal_page_last               206
_journal_paper_doi               10.1039/d4ob01565g
_journal_volume                  23
_journal_year                    2024
_chemical_formula_moiety         'C48 H46 B2 F10 N3 O2 P, C H2 Cl2'
_chemical_formula_sum            'C49 H48 B2 Cl2 F10 N3 O2 P'
_chemical_formula_weight         1024.39
_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_block_doi                 10.5517/ccdc.csd.cc2f6qr4
_audit_creation_date             2022-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-09 deposited with the CCDC.	2024-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                85.586(4)
_cell_angle_beta                 85.395(4)
_cell_angle_gamma                69.910(4)
_cell_formula_units_Z            2
_cell_length_a                   10.5399(5)
_cell_length_b                   11.4428(6)
_cell_length_c                   21.6413(9)
_cell_measurement_reflns_used    3959
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      75.6860
_cell_measurement_theta_min      4.5060
_cell_volume                     2439.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     16.00  44.00   0.50    5.00    --   49.92-109.00 -81.00   56
  2  \w     18.00 102.00   0.50    5.00    --   66.50-109.00 -81.00  168
  3  \w     94.00 133.00   0.50    5.00    --   66.50  57.00   0.00   78
  4  \w     82.00 115.00   0.50    5.00    --   66.50 109.00  14.00   66
  5  \w    -61.00 -22.00   0.50    5.00    --  -53.17  37.00   0.00   78
  6  \w    -60.00  19.00   0.50    5.00    --  -53.17  37.00  30.00  158
  7  \w    -60.00 -20.00   0.50    5.00    --  -53.17 109.00  14.00   80
  8  \w    -69.00 -34.00   0.50    5.00    -- -105.75  57.00 120.00   70
  9  \w    -65.00 -40.00   0.50    5.00    -- -105.75 125.00  60.00   50
 10  \w    -64.00 -37.00   0.50    5.00    -- -105.75 125.00  90.00   54
 11  \w    -98.00 -70.00   0.50    5.00    -- -105.75 125.00  60.00   56
 12  \w   -111.00 -84.00   0.50    5.00    -- -105.75 109.00  14.00   54
 13  \w    -85.00 -58.00   0.50    5.00    -- -105.75  77.00 -30.00   54
 14  \w   -109.00 -36.00   0.50    5.00    -- -105.75  37.00  30.00  146
 15  \w   -117.00 -34.00   0.50    5.00    -- -105.75  57.00  30.00  166
 16  \w   -117.00 -72.00   0.50    5.00    -- -105.75  57.00-120.00   90
 17  \w    -68.00 -36.00   0.50    5.00    -- -105.75  57.00-120.00   64
 18  \w   -113.00 -35.00   0.50    5.00    -- -105.75  19.00-180.00  156
 19  \w   -114.00 -34.00   0.50    5.00    -- -105.75 125.00-150.00  160
 20  \w   -116.00 -84.00   0.50    5.00    -- -105.75 125.00-180.00   64
 21  \w   -123.00 -41.00   0.50    5.00    -- -105.75  77.00-120.00  164
 22  \w   -124.00 -46.00   0.50    5.00    --  -53.17 -19.00-150.00  156
 23  \w   -119.00 -80.00   0.50    5.00    --  -53.17-109.00 -81.00   78
 24  \w   -123.00 -84.00   0.50    5.00    --  -53.17-125.00 -30.00   78
 25  \w   -126.00 -81.00   0.50    5.00    -- -105.75-109.00 -81.00   90
 26  \w   -126.00-100.00   0.50    5.00    -- -105.75 -99.00-150.00   52
 27  \w   -146.00-119.00   0.50    5.00    -- -105.75 -19.00-180.00   54
 28  \w   -173.00-148.00   0.50    5.00    -- -105.75 -99.00-150.00   50
 29  \w   -160.00-133.00   0.50    5.00    -- -105.75-109.00 -81.00   54
 30  \w   -170.00-120.00   0.50    5.00    -- -105.75 -57.00   0.00  100
 31  \w   -159.00 -98.00   0.50    5.00    -- -105.75 -19.00  30.00  122
 32  \w   -117.00 -78.00   0.50    5.00    -- -105.75  57.00 120.00   78
 33  \w   -115.00 -88.00   0.50    5.00    -- -105.75 125.00  90.00   54
 34  \w   -116.00 -54.00   0.50    5.00    -- -105.75 125.00  30.00  124
 35  \w   -177.00-108.00   0.50    5.00    -- -105.75 -57.00  30.00  138
 36  \w   -117.00 -79.00   0.50    5.00    --  -53.17-125.00  60.00   76
 37  \w   -108.00 -83.00   0.50    5.00    -- -105.75 -99.00 150.00   50
 38  \w   -170.00-126.00   0.50    5.00    -- -105.75 -99.00 150.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0876198000
_diffrn_orient_matrix_UB_12      -0.0564175000
_diffrn_orient_matrix_UB_13      -0.0579841000
_diffrn_orient_matrix_UB_21      0.1259998000
_diffrn_orient_matrix_UB_22      -0.0477778000
_diffrn_orient_matrix_UB_23      0.0387001000
_diffrn_orient_matrix_UB_31      -0.0273684000
_diffrn_orient_matrix_UB_32      -0.1230527000
_diffrn_orient_matrix_UB_33      0.0159606000
_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  0.0948
_diffrn_reflns_av_unetI/netI     0.0752
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29927
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.247
_diffrn_reflns_theta_min         4.104
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.212
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55147
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     642
_refine_ls_number_reflns         8887
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1174
_refine_ls_R_factor_gt           0.0721
_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^)+(0.0852P)^2^+1.3789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1647
_refine_ls_wR_factor_ref         0.1892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5774
_reflns_number_total             8887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01565g2.cif
_cod_data_source_block           compound_9a
_cod_depositor_comments
'Adding full bibliography for 7160230--7160235.cif.'
_cod_database_code               7160230
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C98 H94 B4 F22 N6 O4 P4 '
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.809
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C68 \\sim Cl2A-C68
 with sigma of 0.02
3. Others
 Sof(H68C)=Sof(H68D)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl2)=Sof(H68A)=Sof(H68B)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C53(H53), C56(H56), B23(H23)
4.b Secondary CH2 refined with riding coordinates:
 C68(H68A,H68B), C68(H68C,H68D)
4.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C17(H17), C10(H10), C7(H7), C13(H13), C4(H4), C51(H51), C50(H50),
 C11(H11), C5(H5), C49(H49), C12(H12), C6(H6)
4.d Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C60(H60A,H60B,H60C), C66(H66A,H66B,
 H66C), C62(H62A,H62B,H62C), C61(H61A,H61B,H61C), C55(H55A,H55B,H55C), C54(H54A,
 H54B,H54C), C58(H58A,H58B,H58C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              65539
_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 4.412
_oxdiff_exptl_absorpt_empirical_full_min 0.462