The first ring-expanded NHC-copper(i) phosphides as catalysts in the highly selective hydrophosphination of isocyanates.
Horsley Downie, Thomas M.; Hall, Jonathan W.; Collier Finn, Thomas P.; Liptrot, David J.; Lowe, John P.; Mahon, Mary F.; McMullin, Claire L.; Whittlesey, Michael K.; Chemical communications (Cambridge, England) 56 (2020) 13359–13362; doi:10.1039/d0cc05694d

data_7127356
_publ_section_title
;
 The first ring-expanded NHC-copper(i) phosphides as catalysts in the
 highly selective hydrophosphination of isocyanates.
;
_journal_issue                   87
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              13359
_journal_page_last               13362
_journal_paper_doi               10.1039/d0cc05694d
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C41 H50 Cu N2 P S2, C6 H6'
_chemical_formula_sum            'C47 H56 Cu N2 P S2'
_chemical_formula_weight         807.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-03-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-07-06 deposited with the CCDC.	2020-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.7990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.70630(10)
_cell_length_b                   12.65770(10)
_cell_length_c                   32.3409(3)
_cell_measurement_reflns_used    15416
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.1960
_cell_measurement_theta_min      4.1750
_cell_volume                     4331.17(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_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  0.0496
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            31062
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.349
_diffrn_reflns_theta_min         2.765
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.207
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.238
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.178
_exptl_crystal_size_min          0.099
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.404
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         8598
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0445
_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^)+(0.0630P)^2^+1.5629P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1161
_refine_ls_wR_factor_ref         0.1215
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7647
_reflns_number_total             8598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05694d2.cif
_cod_data_source_block           s20djl04
_cod_depositor_comments
'Adding full bibliography for 7127351--7127357.cif.'
_cod_database_code               7127356
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C47-C46 \\sim C45-C44 \\sim C43-C42
 with sigma of 0.005
 C46-C45 \\sim C46A-C45A
 with sigma of 0.02
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C45-C44 \\sim C45A-C44A
 with sigma of 0.02
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C42-C47 \\sim C42A-C47A
 with sigma of 0.02
 C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 C46-C42 \\sim C46A-C42A
 with sigma of 0.04
 C46-C44 \\sim C46A-C44A
 with sigma of 0.04
 C45-C43 \\sim C45A-C43A
 with sigma of 0.04
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 C42-C44 \\sim C42A-C44A
 with sigma of 0.04
 C43-C47 \\sim C43A-C47A
 with sigma of 0.04
3. Others
 Fixed Sof: C42(0.6) H42(0.6) C47(0.6) H47(0.6) C46(0.6) H46(0.6) C45(0.6)
 H45(0.6) C44(0.6) H44(0.6) C43(0.6) H43(0.6) C42A(0.4) H42A(0.4) C47A(0.4)
 H47A(0.4) C46A(0.4) H46A(0.4) C45A(0.4) H45A(0.4) C44A(0.4) H44A(0.4)
 C43A(0.4) H43A(0.4)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C31(H31), C32(H32),
 C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C42(H42), C47(H47), C46(H46), C45(H45), C44(H44), C43(H43), C42A(H42A),
 C47A(H47A), C46A(H46A), C45A(H45A), C44A(H44A), C43A(H43A)
4.d Fitted hexagon refined as free rotating group:
 C42(C47,C46,C45,C44,C43), C42A(C47A,C46A,C45A,C44A,C43A)
4.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C)
;
_shelx_res_checksum              15311
_shelx_hkl_checksum              13590