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_4519022
_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         '2(C20 H18 N O2 P), 1[C7H8]'
_chemical_formula_sum            'C47.01 H44.01 N2 O4 P2'
_chemical_formula_weight         762.91
_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                82.043(2)
_cell_angle_beta                 85.124(2)
_cell_angle_gamma                82.282(2)
_cell_formula_units_Z            1
_cell_length_a                   8.7408(2)
_cell_length_b                   10.3990(3)
_cell_length_c                   11.2630(3)
_cell_measurement_reflns_used    16146
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.9160
_cell_measurement_theta_min      3.9600
_cell_volume                     1002.41(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'PILATUS3 R 200K Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.971
_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  30.00   0.50    1.00    --    0.00 -82.00  30.00  102
  2  \w      7.00  43.00   0.50    1.00    --   34.00  72.00 103.75   72
  3  \w     49.00  76.00   0.50    1.00    --   34.00  72.00 103.75   54
  4  \w      1.00  26.00   0.50    1.00    --   38.00 -40.00-128.20   50
  5  \w     30.00  59.00   0.50    1.00    --   38.00 -40.00-128.20   58
  6  \w    -43.00  -4.00   0.50    1.00    --   38.00 -40.00-128.20   78
  7  \w     17.00  43.00   0.50    1.00    --   42.00  71.00 -36.11   52
  8  \w     63.00  94.00   0.50    1.00    --   42.00  71.00 -36.11   62
  9  \w     13.00  46.00   0.50    1.00    --   42.00  72.00-177.65   66
 10  \w     21.00  61.00   0.50    4.00    --   50.00  72.00-117.67   80
 11  \w     31.00  58.00   0.50    4.00    --   54.00  73.00 -16.33   54
 12  \w    101.00 135.00   0.50    4.00    --   58.00  71.00  81.27   68
 13  \w    115.00 141.00   0.50    4.00    --   58.00  73.00 -86.30   52
 14  \w     30.00  56.00   0.50    4.00    --   58.00  71.00  81.27   52
 15  \w     28.00  56.00   0.50    4.00    --   58.00  73.00 -86.30   56
 16  \w     32.00  67.00   0.50    4.00    --   62.00  73.00 154.37   70
 17  \w     36.00  67.00   0.50    4.00    --   66.00  74.00  83.13   62
 18  \w     36.00  71.00   0.50    4.00    --   66.00  73.00 169.22   70
 19  \w     38.00  64.00   0.50    4.00    --   66.00  70.00 -53.46   52
 20  \w    102.00 149.00   0.50    4.00    --   66.00  70.00 -53.46   94
 21  \w     40.00  80.00   0.50    4.00    --   70.00  75.00 -21.44   80
 22  \w     40.00  72.00   0.50    4.00    --   70.00  73.00  13.33   64
 23  \w     97.00 123.00   0.50    4.00    --   70.00  75.00 -21.44   52
 24  \w    119.00 158.00   0.50    4.00    --   70.00  74.00-179.12   78
 25  \w     40.00  83.00   0.50    4.00    --   70.00  74.00-179.12   86
 26  \w     45.00 103.00   0.50    4.00    --   74.00  71.00  79.48  116
 27  \w     46.00  72.00   0.50    4.00    --   74.00  75.00  32.39   52
 28  \w    138.00 163.00   0.50    4.00    --   74.00  71.00  79.48   50
 29  \w    118.00 161.00   0.50    4.00    --   78.00  71.00-105.35   86
 30  \w     49.00  74.00   0.50    4.00    --   78.00  71.00-105.35   50
 31  \w    118.00 170.00   0.50    4.00    --   82.00  75.00  94.41  104
 32  \w     51.00  96.00   0.50    4.00    --   82.00  75.00  94.41   90
 33  \w     80.00 154.00   0.50    4.00    --   98.00  61.00 120.00  148
 34  \w    125.00 153.00   0.50    4.00    --   98.00  61.00-150.00   56
 35  \w     74.00 186.00   0.50    4.00    --   98.00  61.00   0.00  224
 36  \w     72.00 151.00   0.50    4.00    --   98.00  61.00-120.00  158
 37  \w     72.00 117.00   0.50    4.00    --   98.00  61.00-150.00   90
 38  \w     44.00  71.00   0.50    4.00    --   98.00 -82.00 -30.00   54
 39  \w     11.00 123.00   0.50    4.00    --   98.00 -61.00  90.00  224
 40  \w    152.00 177.00   0.50    4.00    --   98.00  77.00 150.00   50
 41  \w     15.00 120.00   0.50    4.00    --   98.00 -61.00 -60.00  210
 42  \w    115.00 150.00   0.50    4.00    --   98.00  77.00 150.00   70
 43  \w     75.00 166.00   0.50    4.00    --   98.00  61.00  60.00  182
 44  \w     73.00 179.00   0.50    4.00    --   98.00  61.00-180.00  212
 45  \w     39.00  93.00   0.50    4.00    --   98.00 -61.00-150.00  108
 46  \w     18.00 126.00   0.50    4.00    --   98.00 -82.00  90.00  216
 47  \w    133.00 159.00   0.50    4.00    --   98.00  61.00 -30.00   52
 48  \w     72.00 116.00   0.50    4.00    --   98.00  61.00 -30.00   88
 49  \w     62.00 131.00   0.50    4.00    --   98.00 -82.00-150.00  138
 50  \w    150.00 176.00   0.50    4.00    --   98.00  65.00 138.83   52
 51  \w     73.00 123.00   0.50    4.00    --   98.00  65.00 138.83  100
 52  \w     12.00  51.00   0.50    4.00    --   98.00 -82.00-150.00   78
 53  \w    127.00 181.00   0.50    4.00    --   98.00  61.00  30.00  108
 54  \w     77.00 116.00   0.50    4.00    --   98.00 -82.00 -30.00   78
 55  \w     73.00 116.00   0.50    4.00    --   98.00  61.00  30.00   86
 56  \w    132.00 165.00   0.50    4.00    --   98.00  61.00 -60.00   66
 57  \w    133.00 177.00   0.50    4.00    --   98.00  61.00 -90.00   88
 58  \w     72.00 120.00   0.50    4.00    --   98.00  61.00 -90.00   96
 59  \w     72.00 114.00   0.50    4.00    --   98.00  61.00 -60.00   84
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtalLAB PRO MM007, PILATUS3 R 200K'
_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      -0.0034813000
_diffrn_orient_matrix_UB_12      0.0454594000
_diffrn_orient_matrix_UB_13      -0.1359711000
_diffrn_orient_matrix_UB_21      -0.1341038000
_diffrn_orient_matrix_UB_22      -0.0805277000
_diffrn_orient_matrix_UB_23      -0.0061109000
_diffrn_orient_matrix_UB_31      -0.1174043000
_diffrn_orient_matrix_UB_32      0.1190591000
_diffrn_orient_matrix_UB_33      0.0252343000
_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  0.0215
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20755
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.323
_diffrn_reflns_theta_min         3.972
_diffrn_source                   'rotating anode'
_diffrn_source_type              'MicroMax 007 HF'
_exptl_absorpt_coefficient_mu    1.354
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.615
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.264
_exptl_crystal_description       cube
_exptl_crystal_F_000             402
_exptl_crystal_recrystallization_method
'Recrystalised from 3 toluene : 1 ethanol at -30C.'
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.198
_exptl_crystal_size_min          0.167
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         4008
_refine_ls_number_restraints     1089
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0352
_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^)+(0.0436P)^2^+0.4303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3851
_reflns_number_total             4008
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc1c02907_si_002.cif
_cod_data_source_block           ochdkj
_cod_database_code               4519022
_nottingham_internal_coll_name   OCHDKJ
_nottingham_internal_coll_number 18863
_nottingham_internal_coll_client CH/DLK
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '1.00, 4.00'
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pcxch6
_nottingham_internal_coll_date   27/11/2020
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 03/12/2020
_nottingham_internal_process_user pcxch6
_nottingham_internal_solution_date 13/2/2021
_nottingham_internal_solution_user pcxch6
_nottingham_internal_refinement_date 13/2/2021
_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
'OCHDKJ #18863 MM-733 for CH/DLK in fomblin film on a micromount'
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.686
_reflns_odcompleteness_completeness 99.69
_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 C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C27-C21
 1.51 with sigma of 0.02
 C21-C26 = C21-C22 = C25-C24
 1.39 with sigma of 0.02
 C26-C25 = C24-C23 = C23-C22
 1.38 with sigma of 0.02
 N1-H1
 0.88 with sigma of 0.02
 C21-C25
 2.42 with sigma of 0.04
 C26-C24
 2.39 with sigma of 0.04
 C21-C23
 2.41 with sigma of 0.04
 C25-C23 = C24-C22
 2.4 with sigma of 0.04
 C27-C26 = C27-C22
 2.52 with sigma of 0.04
 N1-C14B \\sim N1-C14A \\sim N1-C14C
 with sigma of 0.01
 C21-C26 \\sim C26-C25 \\sim C25-C24 \\sim C24-C23 \\sim C23-C22 \\sim C22-C21
 with sigma of 0.02
 C21-C23 \\sim C21-C25 \\sim C22-C24 \\sim C26-C22 \\sim C25-C23 \\sim C26-C24
 with sigma of 0.04
 C27-C22 \\sim C27-C26
 with sigma of 0.04
 C15B-C14B \\sim C15C-C14C \\sim C15A-C14A
 with sigma of 0.01
 N1-C15A \\sim N1-C15B \\sim N1-C15C
 with sigma of 0.02
3. Restrained planarity
 C15C, C16C, C17C, C18C, C19C, C20C
 with sigma of 0.1
 C15A, C16A, C17A, C18A, C19A, C20A
 with sigma of 0.1
 C15B, C16B, C17B, C18B, C19B, C20B
 with sigma of 0.1
 C14C, C15C, C16C, C20C
 with sigma of 0.1
 C14B, C15B, C16B, C20B
 with sigma of 0.1
 C14A, C15A, C16A, C20A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C14A \\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim
C14B \\sim C15B \\sim C16B \\sim C17B \\sim C18B \\sim C19B \\sim C20B \\sim
C14C \\sim C15C \\sim C16C \\sim C17C \\sim C18C \\sim C19C \\sim C20C: within
2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27: within 2.5A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
Uanis(C14B) = Uanis(C14C) = Uanis(C14A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C14A, C15A, C20A, C19A, C18A, C17A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C14A, C15A, C16A, C17A, C18A, C19A, C20A}
{C14A, C15A, C20A, C19A, C18A, C17A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
{C14A, C15A, C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C14B, C15B, C16B, C17B, C18B, C19B, C20B}
{C14A, C15A, C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
{C14A, C15A, C20A, C19A, C18A, C17A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C14C, C15C, C16C, C17C, C18C, C19C, C20C}
7. Others
 1*[Sof(C14B)+Sof(H14C)+Sof(H14D)+Sof(C15B)+Sof(C16B)+Sof(H16B)+Sof(C17B)+
 Sof(H17B)+Sof(C18B)+Sof(H18B)+Sof(C19B)+Sof(H19B)+Sof(C20B)+Sof(H20B)]+1*
 [Sof(C14A)+Sof(H14A)+Sof(H14B)+Sof(C15A)+Sof(C16A)+Sof(H16A)+Sof(C17A)+
 Sof(H17A)+Sof(C18A)+Sof(H18A)+Sof(C19A)+Sof(H19A)+Sof(C20A)+Sof(H20A)]+1*
 [Sof(C14C)+Sof(H14E)+Sof(H14F)+Sof(C15C)+Sof(C16C)+Sof(H16C)+Sof(C17C)+
 Sof(H17C)+Sof(C18C)+Sof(H18C)+Sof(C19C)+Sof(H19C)+Sof(C20C)+Sof(H20C)]=1 with
 esd of 0.001
 Sof(C14B)=Sof(H14C)=Sof(H14D)=Sof(C15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=
 Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20B)=FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=FVAR(2)
 Sof(C14C)=Sof(H14E)=Sof(H14F)=Sof(C15C)=Sof(C16C)=Sof(H16C)=Sof(C17C)=
 Sof(H17C)=Sof(C18C)=Sof(H18C)=Sof(C19C)=Sof(H19C)=Sof(C20C)=Sof(H20C)=FVAR(3)
 Fixed Sof: C21(0.5) C22(0.5) H22(0.5) C23(0.5) H23(0.5) C24(0.5) H24(0.5)
 C25(0.5) H25(0.5) C26(0.5) H26(0.5) C27(0.5) H27A(0.5) H27B(0.5) H27C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C14A(H14A,H14B), C14B(H14C,H14D), C14C(H14E,H14F)
8.b 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), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C16A(H16A),
 C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C20B(H20B), C16C(H16C), C17C(H17C), C18C(H18C),
 C19C(H19C), C20C(H20C)
8.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C)
;
_shelx_res_checksum              10367
_shelx_hkl_checksum              27778
_olex2_date_sample_data_collection 2021-12-03
_olex2_date_sample_submission    2020-09-09
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id OCHDKJ
_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 1.791
_oxdiff_exptl_absorpt_empirical_full_min 0.498