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_4519025
_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         'C20 H18 N O2 P S'
_chemical_formula_sum            'C20 H18 N O2 P S'
_chemical_formula_weight         367.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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
_cell_angle_beta                 104.7200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.19830(10)
_cell_length_b                   10.78100(10)
_cell_length_c                   13.91420(10)
_cell_measurement_reflns_used    24294
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.5050
_cell_measurement_theta_min      3.7270
_cell_volume                     1769.80(3)
_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 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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     -5.00  35.00   1.00    5.00    --  -42.12  19.00  90.00   40
  2  \w     -5.00  35.00   1.00    5.00    --  -42.12  19.00 -60.00   40
  3  \w     -5.00  35.00   1.00    5.00    --  -42.12  19.00 -90.00   40
  4  \w     17.00 112.00   1.00    5.00    --   42.12  57.00 -60.00   95
  5  \w    -21.00  74.00   1.00    5.00    --   42.12 -77.00 150.00   95
  6  \w     31.00  93.00   1.00   20.00    --  101.44 -61.00 150.00   62
  7  \w     77.00 172.00   1.00   20.00    --  101.44  45.00 -90.00   95
  8  \w     97.00 175.00   1.00   20.00    --  101.44 125.00 -90.00   78
  9  \w     35.00 125.00   1.00   20.00    --  101.44-141.00 -60.00   90
 10  \w     28.00  57.00   1.00   20.00    --  101.44 -30.00   0.00   29
 11  \w     28.00 113.00   1.00   20.00    --  101.44-125.00 150.00   85
 12  \w     28.00  57.00   1.00   20.00    --  101.44 -30.00-150.00   29
 13  \w     77.00 171.00   1.00   20.00    --  101.44  50.00 -27.65   94
 14  \w     77.00 172.00   1.00   20.00    --  101.44  45.00  30.00   95
 15  \w     27.00 127.00   1.00   20.00    --  101.44 -77.00 -90.00  100
 16  \w     -5.00  35.00   1.00    5.00    --  -42.12  19.00  60.00   40
 17  \w      9.00  42.00   1.00    5.00    --   42.12  81.00-119.28   33
 18  \w     18.00 114.00   1.00    5.00    --   42.12  38.00-180.00   96
 19  \w     17.00 112.00   1.00    5.00    --   42.12  57.00  60.00   95
 20  \w     75.00 171.00   1.00   20.00    --  101.44  61.00 150.00   96
 21  \w     75.00 171.00   1.00   20.00    --  101.44  61.00-156.05   96
 22  \w     75.00 171.00   1.00   20.00    --  101.44  61.00  90.00   96
 23  \w     75.00 171.00   1.00   20.00    --  101.44  61.00  60.00   96
 24  \w     62.00 178.00   1.00   20.00    --  101.44  15.00-180.00  116
 25  \w     72.00 173.00   1.00   20.00    --  101.44  70.00 -84.34  101
 26  \w     31.00  93.00   1.00   20.00    --  101.44 -61.00   0.00   62
 27  \w     31.00  72.00   1.00   20.00    --  101.44 -45.00 -60.00   41
 28  \w     13.00 113.00   1.00    5.00    --   42.12  69.00 106.37  100
 29  \w      6.00  82.00   1.00    5.00    --   42.12 -99.00 -30.00   76
 30  \w     10.00  42.00   1.00    5.00    --   42.12  80.00 171.40   32
 31  \w     10.00  42.00   1.00    5.00    --   42.12  80.00 -28.16   32
 32  \w     75.00 171.00   1.00   20.00    --  101.44  61.00-180.00   96
 33  \w     77.00 172.00   1.00   20.00    --  101.44  45.00-120.00   95
 34  \w     74.00 171.00   1.00   20.00    --  101.44  62.00 -17.62   97
 35  \w     75.00 171.00   1.00   20.00    --  101.44  61.00  30.00   96
 36  \w     75.00 171.00   1.00   20.00    --  101.44  61.00 120.00   96
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan 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      0.0089626000
_diffrn_orient_matrix_UB_12      -0.0715813000
_diffrn_orient_matrix_UB_13      0.0974265000
_diffrn_orient_matrix_UB_21      -0.0383433000
_diffrn_orient_matrix_UB_22      -0.1195282000
_diffrn_orient_matrix_UB_23      -0.0598070000
_diffrn_orient_matrix_UB_31      0.1245825000
_diffrn_orient_matrix_UB_32      -0.0317191000
_diffrn_orient_matrix_UB_33      0.0051626000
_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  0.0194
_diffrn_reflns_av_unetI/netI     0.0092
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            32597
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.384
_diffrn_reflns_theta_min         4.310
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.586
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.760
_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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             768
_exptl_crystal_recrystallization_method
'recrystalised from ethanol: THF, 1:4 at -30C'
_exptl_crystal_size_max          0.152
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.103
_refine_diff_density_max         0.379
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         3481
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0254
_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^)+(0.0326P)^2^+1.0409P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0664
_refine_ls_wR_factor_ref         0.0666
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3434
_reflns_number_total             3481
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkd
_cod_database_code               4519025
_nottingham_internal_coll_name   OCHDKD
_nottingham_internal_coll_number 18738
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '20.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   22/07/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 30/07/2020
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 03/08/2020
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 03/08/2020
_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         C20H18N1O2P1S1
_chemical_oxdiff_usercomment
'OCHDKD #18738 GVA-1809 CH/DLK fomblin micromount'
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.695
_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
 At 1.5 times of:
  All C(H,H,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), C18(H18), C19(H19)
3.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              60444
_shelx_hkl_checksum              41081
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKD
_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 1.543
_oxdiff_exptl_absorpt_empirical_full_min 0.827