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_4519020
_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         'C15 H16 N O2 P'
_chemical_formula_sum            'C15 H16 N O2 P'
_chemical_formula_weight         273.26
_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                90.450(3)
_cell_angle_beta                 93.891(3)
_cell_angle_gamma                117.301(4)
_cell_formula_units_Z            4
_cell_length_a                   8.7838(4)
_cell_length_b                   8.7951(4)
_cell_length_c                   20.4442(8)
_cell_measurement_reflns_used    9535
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.4220
_cell_measurement_theta_min      4.3470
_cell_volume                     1398.88(12)
_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  (Sheldrick, 2015)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.979
_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     -4.00  21.00   1.00    4.00    --   34.00  91.00 178.08   25
  2  \w     -5.00  20.00   1.00    4.00    --   34.00  94.00  87.64   25
  3  \w   -112.00 -13.00   1.00    4.00    --  -40.95 -57.00 150.00   99
  4  \w     58.00 101.00   1.00    4.00    --   40.95  38.00 -30.00   43
  5  \w    -29.00  69.00   1.00    4.00    --   40.95 -57.00  30.00   98
  6  \w     25.00  56.00   1.00    4.00    --   40.95  38.00 -30.00   31
  7  \w     28.00  97.00   1.00    4.00    --   40.95-125.00 -60.00   69
  8  \w      7.00  32.00   1.00    4.00    --   42.00  84.00 -29.01   25
  9  \w     16.00  41.00   1.00    4.00    --   50.00  82.00-118.59   25
 10  \w     16.00  41.00   1.00    4.00    --   50.00  81.00-168.19   25
 11  \w     16.00  41.00   1.00    4.00    --   50.00  81.00  31.84   25
 12  \w     16.00  41.00   1.00    4.00    --   50.00  82.00 -38.62   25
 13  \w     16.00  41.00   1.00    4.00    --   50.00  82.00  41.65   25
 14  \w     16.00  41.00   1.00    4.00    --   50.00  81.00-133.72   25
 15  \w     16.00  41.00   1.00    4.00    --   50.00  82.00 128.30   25
 16  \w     23.00  50.00   1.00    4.00    --   54.00  71.00  17.80   27
 17  \w     64.00 128.00   1.00    4.00    --   54.00  71.00  17.80   64
 18  \w     25.00  52.00   1.00    4.00    --   54.00  74.00 102.46   27
 19  \w     96.00 122.00   1.00    4.00    --   54.00  74.00 102.46   26
 20  \w     92.00 131.00   1.00    4.00    --   58.00  74.00  54.49   39
 21  \w     28.00  55.00   1.00    4.00    --   58.00  74.00  54.49   27
 22  \w     30.00  61.00   1.00    4.00    --   62.00  74.00 108.47   31
 23  \w     33.00  60.00   1.00    4.00    --   62.00  71.00 159.17   27
 24  \w    109.00 134.00   1.00    4.00    --   62.00  74.00 108.47   25
 25  \w     97.00 134.00   1.00    4.00    --   62.00  71.00 159.17   37
 26  \w     34.00  61.00   1.00    4.00    --   66.00  74.00 -77.72   27
 27  \w     36.00  64.00   1.00    4.00    --   66.00  64.00-104.30   28
 28  \w     37.00  76.00   1.00    4.00    --   66.00  68.00   8.39   39
 29  \w     39.00  73.00   1.00    4.00    --   70.00  73.00 175.70   34
 30  \w     43.00  69.00   1.00    4.00    --   70.00  54.00 155.70   26
 31  \w     44.00  76.00   1.00   16.00    --   74.00  66.00  49.23   32
 32  \w    101.00 149.00   1.00   16.00    --   74.00  73.00 -61.02   48
 33  \w     42.00  69.00   1.00   16.00    --   74.00  73.00 -61.02   27
 34  \w    121.00 148.00   1.00   16.00    --   78.00  64.00 -39.95   27
 35  \w     51.00  84.00   1.00   16.00    --   78.00  64.00 -39.95   33
 36  \w     52.00  91.00   1.00   16.00    --   82.00  65.00-142.70   39
 37  \w     58.00  86.00   1.00   16.00    --   86.00  62.00  93.02   28
 38  \w     75.00 171.00   1.00   16.00    --  104.05  61.00  90.00   96
 39  \w    129.00 173.00   1.00   16.00    --  104.05 125.00   0.00   44
 40  \w     31.00 112.00   1.00   16.00    --  104.05-125.00 -30.00   81
 41  \w     76.00 103.00   1.00   16.00    --  104.05  61.00  30.00   27
 42  \w     68.00 111.00   1.00   16.00    --  104.05-125.00  30.00   43
 43  \w     75.00 172.00   1.00   16.00    --  104.05  61.00   0.00   97
 44  \w     75.00 171.00   1.00   16.00    --  104.05  61.00-150.00   96
 45  \w     75.00 159.00   1.00   16.00    --  104.05  61.00 120.00   84
 46  \w    116.00 141.00   1.00   16.00    --  104.05  61.00  60.00   25
 47  \w     75.00 102.00   1.00   16.00    --  104.05  61.00  60.00   27
 48  \w     30.00  85.00   1.00   16.00    --  104.05 -77.00 -30.00   55
 49  \w    114.00 175.00   1.00   16.00    --  104.05  61.00 150.00   61
 50  \w     83.00 112.00   1.00   16.00    --  104.05-125.00-120.00   29
 51  \w     76.00 102.00   1.00   16.00    --  104.05  61.00 150.00   26
 52  \w     32.00  81.00   1.00   16.00    --  104.05-125.00-120.00   49
 53  \w     75.00 176.00   1.00   16.00    --  104.05  61.00 -90.00  101
 54  \w    117.00 144.00   1.00   16.00    --  104.05  61.00 -30.00   27
 55  \w     75.00 104.00   1.00   16.00    --  104.05  61.00 -30.00   29
 56  \w    129.00 156.00   1.00   16.00    --  104.05  61.00-180.00   27
 57  \w    112.00 175.00   1.00   16.00    --  104.05  61.00  30.00   63
 58  \w     28.00 117.00   1.00   16.00    --  104.05 -77.00  90.00   89
 59  \w     75.00 114.00   1.00   16.00    --  104.05  61.00-180.00   39
 60  \w     76.00 154.00   1.00   16.00    --  104.05  61.00-120.00   78
 61  \w    119.00 176.00   1.00   16.00    --  104.05  61.00 -60.00   57
 62  \w     75.00 107.00   1.00   16.00    --  104.05  61.00 -60.00   32
 63  \w     24.00 107.00   1.00   16.00    --  104.05 -94.00  60.00   83
;
_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      -0.0398021000
_diffrn_orient_matrix_UB_12      0.1501229000
_diffrn_orient_matrix_UB_13      0.0136117000
_diffrn_orient_matrix_UB_21      0.1900405000
_diffrn_orient_matrix_UB_22      0.1141018000
_diffrn_orient_matrix_UB_23      0.0236856000
_diffrn_orient_matrix_UB_31      0.0391497000
_diffrn_orient_matrix_UB_32      0.0580998000
_diffrn_orient_matrix_UB_33      -0.0704835000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            7807
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.753
_diffrn_reflns_theta_min         4.339
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.721
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.537
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method 'Recystallised from ethanol'
_exptl_crystal_size_max          0.284
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         7807
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0688P)^2^+0.2094P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1038
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6791
_reflns_number_total             7807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkb
_cod_original_cell_volume        1398.88(11)
_cod_database_code               4519020
_nottingham_internal_coll_name   OCHDKB
_nottingham_internal_coll_number 18736
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '16.00, 4.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczlt
_nottingham_internal_coll_date   20/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 06/08/2020
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 06/08/2020
_nottingham_internal_solution_user pczlt
_nottingham_internal_refinement_date 06/08/2020
_nottingham_internal_refinement_user pczlt
_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         C15H16N1O2P
_chemical_oxdiff_usercomment
'OCHDKB #18736 GVB-1803 CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.641
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5320(9)
 0.4680(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
 N2-H2A
 0.88 with sigma of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C14(H14A,H14B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C4(H4), C23(H23), C18(H18), C9(H9), C24(H24), C3(H3),
 C21(H21), C27(H27), C12(H12), C6(H6), C17(H17), C25(H25), C10(H10), C26(H26),
 C19(H19), C20(H20), C11(H11), C5(H5)
4.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              85529
_shelx_hkl_checksum              21242
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKB
_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 1.365
_oxdiff_exptl_absorpt_empirical_full_min 0.763