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_4519018
_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         'C19 H15 F N O2 P'
_chemical_formula_sum            'C19 H15 F N O2 P'
_chemical_formula_weight         339.29
_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                80.225(3)
_cell_angle_beta                 85.954(3)
_cell_angle_gamma                77.248(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6254(3)
_cell_length_b                   8.9016(3)
_cell_length_c                   10.8499(3)
_cell_measurement_reflns_used    7564
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.4960
_cell_measurement_theta_min      4.0980
_cell_volume                     800.24(5)
_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 1.000
_diffrn_measured_fraction_theta_max 0.988
_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      2.00  27.00   1.00    2.00    --   38.00  87.00  10.05   25
  2  \w      3.00  29.00   1.00    2.00    --   38.00  86.00-110.08   26
  3  \w      2.00  28.00   1.00    2.00    --   38.00  90.00 109.76   26
  4  \w   -113.00 -55.00   1.00    2.00    --  -41.70 -57.00  60.00   58
  5  \w    -51.00 -14.00   1.00    2.00    --  -41.70 -57.00  60.00   37
  6  \w   -114.00 -21.00   1.00    2.00    --  -41.70 -38.00 -60.00   93
  7  \w     -8.00  23.00   1.00    2.00    --  -41.70  38.00 120.00   31
  8  \w     27.00  93.00   1.00    2.00    --   41.70-125.00-180.00   66
  9  \w    -28.00  65.00   1.00    2.00    --   41.70 -57.00 -60.00   93
 10  \w      8.00  33.00   1.00    2.00    --   42.00  83.00-140.86   25
 11  \w     13.00  38.00   1.00    2.00    --   46.00  81.00 149.18   25
 12  \w     31.00  79.00   1.00    2.00    --   58.00  55.00-151.16   48
 13  \w     28.00  58.00   1.00    2.00    --   58.00  74.00  30.97   30
 14  \w     32.00  58.00   1.00    2.00    --   62.00  64.00  67.83   26
 15  \w     32.00  66.00   1.00    2.00    --   62.00  72.00  91.13   34
 16  \w     32.00  70.00   1.00    2.00    --   62.00  74.00-118.00   38
 17  \w     31.00  57.00   1.00    2.00    --   62.00  72.00 -69.45   26
 18  \w     32.00  59.00   1.00    2.00    --   62.00  72.00 -12.27   27
 19  \w     34.00  60.00   1.00    2.00    --   66.00  74.00-166.30   26
 20  \w     35.00  63.00   1.00    2.00    --   66.00  73.00 136.70   28
 21  \w    103.00 134.00   1.00    5.00    --   74.00  63.00  -6.26   31
 22  \w     50.00  76.00   1.00    5.00    --   74.00  63.00  -6.26   26
 23  \w     46.00  75.00   1.00    5.00    --   74.00  60.00 124.76   29
 24  \w     43.00  69.00   1.00    5.00    --   74.00  71.00 -47.40   26
 25  \w     89.00 146.00   1.00    5.00    --   82.00  66.00-157.46   57
 26  \w     52.00  78.00   1.00    5.00    --   82.00  66.00-157.46   26
 27  \w     88.00 151.00   1.00    5.00    --   86.00  66.00  26.18   63
 28  \w     58.00  84.00   1.00    5.00    --   86.00  66.00  26.18   26
 29  \w     63.00  90.00   1.00    5.00    --   86.00  51.00   6.33   27
 30  \w     60.00  91.00   1.00    5.00    --   90.00  64.00 122.00   31
 31  \w     75.00 175.00   1.00    5.00    --  104.05  61.00 150.00  100
 32  \w     32.00  72.00   1.00    5.00    --  104.05 -45.00 -90.00   40
 33  \w     34.00  93.00   1.00    5.00    --  104.05 -61.00  60.00   59
 34  \w     78.00 120.00   1.00    5.00    --  104.05  45.00   0.00   42
 35  \w     75.00 130.00   1.00    5.00    --  104.05  61.00  60.00   55
 36  \w     75.00 176.00   1.00    5.00    --  104.05  61.00 -60.00  101
 37  \w     60.00 110.00   1.00    5.00    --  104.05-125.00-150.00   50
 38  \w    118.00 158.00   1.00    5.00    --  104.05  61.00 -90.00   40
 39  \w     27.00  79.00   1.00    5.00    --  104.05 -94.00-120.00   52
 40  \w     76.00 102.00   1.00    5.00    --  104.05  61.00 -90.00   26
 41  \w     76.00 102.00   1.00    5.00    --  104.05  61.00-180.00   26
 42  \w     30.00 108.00   1.00    5.00    --  104.05-104.00  15.79   78
 43  \w     77.00 145.00   1.00    5.00    --  104.05  61.00 120.00   68
 44  \w    115.00 166.00   1.00    5.00    --  104.05  71.00-166.25   51
 45  \w     31.00 108.00   1.00    5.00    --  104.05-125.00 -30.00   77
 46  \w    123.00 176.00   1.00    5.00    --  104.05  61.00  30.00   53
 47  \w     74.00 110.00   1.00    5.00    --  104.05  71.00-166.25   36
 48  \w     77.00 108.00   1.00    5.00    --  104.05  61.00  30.00   31
 49  \w     75.00 134.00   1.00    5.00    --  104.05  61.00  90.00   59
 50  \w     75.00 161.00   1.00    5.00    --  104.05  61.00-120.00   86
 51  \w     79.00 106.00   1.00    5.00    --  104.05 -94.00  60.00   27
 52  \w     34.00  74.00   1.00    5.00    --  104.05 -94.00  60.00   40
 53  \w     32.00  64.00   1.00    5.00    --  104.05-125.00-120.00   32
 54  \w     87.00 112.00   1.00    5.00    --  104.05-125.00-120.00   25
 55  \w     75.00 152.00   1.00    5.00    --  104.05  61.00   0.00   77
;
_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      -0.0189614000
_diffrn_orient_matrix_UB_12      0.1675032000
_diffrn_orient_matrix_UB_13      -0.0718527000
_diffrn_orient_matrix_UB_21      -0.0329479000
_diffrn_orient_matrix_UB_22      0.0644272000
_diffrn_orient_matrix_UB_23      0.1245654000
_diffrn_orient_matrix_UB_31      0.1792455000
_diffrn_orient_matrix_UB_32      -0.0094494000
_diffrn_orient_matrix_UB_33      0.0102242000
_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  0.0250
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            12745
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.607
_diffrn_reflns_theta_min         4.137
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.719
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.800
_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    1.408
_exptl_crystal_description       block
_exptl_crystal_F_000             352
_exptl_crystal_recrystallization_method '2:1 THF:ethanol at -30C'
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.037
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         3141
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0291P)^2^+0.4088P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0714
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2941
_reflns_number_total             3141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkl
_cod_database_code               4519018
_nottingham_internal_coll_name   OCHDKL
_nottingham_internal_coll_number 18865
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '2.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   27/11/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 03/12/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 14/10/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 14/10/2020
_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         'C20 H18 N1 O2 P1'
_chemical_oxdiff_usercomment
'OCHDKL #18865 GVB-1859 for CH/DLK in fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.739
_reflns_odcompleteness_completeness 100.00
_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
2. Restrained distances
 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), C16(H16), C17(H17), C18(H18)
;
_shelx_res_checksum              61160
_shelx_hkl_checksum              5235
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKL
_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 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.836