Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates under Low-Added-Solvent Conditions
Huke, Cameron D.; Taylor, Laurence J.; Argent, Stephen P.; Kays, Deborah L.; ACS Sustainable Chemistry & Engineering 9 (2021) 10704–10709; doi:10.1021/acssuschemeng.1c02907

data_4519019
_publ_section_title
;
 Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates
 under Low-Added-Solvent Conditions
;
_journal_issue                   32
_journal_name_full               'ACS Sustainable Chemistry &amp; Engineering'
_journal_page_first              10704
_journal_page_last               10709
_journal_paper_doi               10.1021/acssuschemeng.1c02907
_journal_volume                  9
_journal_year                    2021
_chemical_formula_moiety         'C21 H20 N O4 P'
_chemical_formula_sum            'C21 H20 N O4 P'
_chemical_formula_weight         381.35
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-02-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_cell_angle_alpha                102.974(4)
_cell_angle_beta                 93.417(4)
_cell_angle_gamma                104.758(4)
_cell_formula_units_Z            4
_cell_length_a                   11.1796(4)
_cell_length_b                   12.4375(6)
_cell_length_c                   14.5087(7)
_cell_measurement_reflns_used    7153
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.4770
_cell_measurement_theta_min      4.7650
_cell_volume                     1886.37(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.972
_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    -21.00   4.00   1.00   10.00    --  -41.95  38.00 150.00   25
  2  \w      5.00  33.00   1.00   10.00    --  -41.95  19.00 -60.00   28
  3  \w      3.00  34.00   1.00   10.00    --  -41.95  19.00-150.00   31
  4  \w     -3.00  32.00   1.00   10.00    --  -41.95  19.00-120.00   35
  5  \w      0.00  38.00   1.00   10.00    --  -41.95  19.00-180.00   38
  6  \w     11.00  36.00   1.00   10.00    --  -41.95  19.00 150.00   25
  7  \w     -3.00  37.00   1.00   10.00    --  -41.95  19.00 -90.00   40
  8  \w      8.00  84.00   1.00   10.00    --   41.95-102.00  50.00   76
  9  \w     37.00  91.00   1.00   10.00    --   41.95-125.00 -60.00   54
 10  \w     43.00  72.00   1.00   40.00    --  104.05 -45.00  30.00   29
 11  \w     49.00 124.00   1.00   40.00    --  104.05 -77.00  90.00   75
 12  \w     40.00 112.00   1.00   40.00    --  104.05-125.00   0.00   72
 13  \w     26.00  53.00   1.00   40.00    --  104.05-102.00  50.00   27
 14  \w     77.00 108.00   1.00   40.00    --  104.05-102.00  50.00   31
 15  \w     21.00 175.00   1.00   40.00    --  104.05   0.00-120.00  154
 16  \w     29.00  56.00   1.00   40.00    --  104.05 -30.00  60.00   27
 17  \w     32.00  59.00   1.00   40.00    --  104.05 -61.00  30.00   27
 18  \w     36.00  72.00   1.00   40.00    --  104.05 -45.00-150.00   36
 19  \w     23.00 107.00   1.00   40.00    --  104.05 -94.00-120.00   84
 20  \w     29.00  54.00   1.00   40.00    --  104.05 -30.00 120.00   25
 21  \w     35.00  71.00   1.00   40.00    --  104.05 -45.00 -60.00   36
 22  \w     34.00  59.00   1.00   40.00    --  104.05 -45.00 150.00   25
 23  \w    113.00 178.00   1.00   40.00    --  104.05  77.00  60.00   65
 24  \w     81.00 124.00   1.00   40.00    --  104.05 -77.00 -60.00   43
 25  \w     81.00 106.00   1.00   40.00    --  104.05 -97.00 165.63   25
 26  \w     23.00  56.00   1.00   40.00    --  104.05 -97.00 165.63   33
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1393291000
_diffrn_orient_matrix_UB_12      -0.0095820000
_diffrn_orient_matrix_UB_13      -0.0223259000
_diffrn_orient_matrix_UB_21      -0.0003409000
_diffrn_orient_matrix_UB_22      0.0684705000
_diffrn_orient_matrix_UB_23      0.1025747000
_diffrn_orient_matrix_UB_31      0.0347990000
_diffrn_orient_matrix_UB_32      0.1127162000
_diffrn_orient_matrix_UB_33      -0.0322213000
_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  0.0158
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13756
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.831
_diffrn_reflns_theta_min         3.794
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.520
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.902
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_recrystallization_method 'Recrystalised from THF at -30C.'
_exptl_crystal_size_max          0.109
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     497
_refine_ls_number_reflns         7290
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0368P)^2^+0.8351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0798
_refine_ls_wR_factor_ref         0.0830
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6491
_reflns_number_total             7290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkf
_cod_original_cell_volume        1886.37(15)
_cod_database_code               4519019
_nottingham_internal_coll_name   OCHDKF
_nottingham_internal_coll_number 18758
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '10.00, 40.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   29/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 05/08/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 25/08/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 25/08/2020
_nottingham_internal_refinement_user pcxch6
_nottingham_internal_self_archive_date 16/02/2021
_nottingham_internal_self_validation_date 16/02/2021
_nottingham_internal_self_validation_user pcxch6
_nottingham_internal_validation_date 17/02/2021
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 17/02/2021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H20N1O4P1
_chemical_oxdiff_usercomment
'OCHDKF #18758 GVB-1810 CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.852
_reflns_odcompleteness_completeness 99.90
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2A
 0.88 with sigma of 0.02
 N1-H1
 0.88 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C15(H15), C17(H17), C19(H19), C23(H23), C24(H24), C25(H25), C26(H26),
  C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C36(H36),
 C38(H38), C40(H40)
3.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C)
;
_shelx_res_checksum              49629
_shelx_hkl_checksum              47843
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKF
_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 1.126
_oxdiff_exptl_absorpt_empirical_full_min 0.863