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_7127352
_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         '2(C47 H55 Cu N3 P S), 2(C6 H6)'
_chemical_formula_sum            'C106 H122 Cu2 N6 P2 S2'
_chemical_formula_weight         1733.23
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-07-06 deposited with the CCDC.	2020-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                99.1230(10)
_cell_angle_beta                 103.295(2)
_cell_angle_gamma                92.374(2)
_cell_formula_units_Z            2
_cell_length_a                   16.7653(4)
_cell_length_b                   16.7976(3)
_cell_length_c                   17.4582(3)
_cell_measurement_reflns_used    23688
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.2070
_cell_measurement_theta_min      2.6760
_cell_volume                     4708.68(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_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 0.982
_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           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0206
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            39170
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.418
_diffrn_reflns_theta_min         2.673
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.669
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95464
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.175
_exptl_crystal_size_min          0.152
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.719
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1121
_refine_ls_number_reflns         18602
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0390P)^2^+1.9290P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0862
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16924
_reflns_number_total             18602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05694d2.cif
_cod_data_source_block           s20djl03
_cod_depositor_comments
'Adding full bibliography for 7127351--7127357.cif.'
_cod_database_code               7127352
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'pale yellow block'
_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
 Cu1-S1 \\sim Cu1-S1A
 with sigma of 0.02
 S1-C29 \\sim S1A-C29
 with sigma of 0.02
 C101-C106 \\sim C1B-C1C
 with sigma of 0.02
 C101-C102 \\sim C1B-C1A
 with sigma of 0.02
 C106-C105 \\sim C1C-C1D
 with sigma of 0.02
 C105-C104 \\sim C1D-C1E
 with sigma of 0.02
 C104-C103 \\sim C1E-C1F
 with sigma of 0.02
 C103-C102 \\sim C1F-C1A
 with sigma of 0.02
 C101-C105 \\sim C1B-C1D
 with sigma of 0.04
 C101-C103 \\sim C1B-C1F
 with sigma of 0.04
 C106-C104 \\sim C1C-C1E
 with sigma of 0.04
 C106-C102 \\sim C1C-C1A
 with sigma of 0.04
 C105-C103 \\sim C1D-C1F
 with sigma of 0.04
 C104-C102 \\sim C1E-C1A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(S1) = Uanis(S1A)
4. Others
 1*[Sof(Cu1)+Sof(P1)+Sof(N1)+Sof(N2)+Sof(N3)+Sof(C1)+Sof(C2)+Sof(H2A)+Sof(H2B)+
 Sof(C3)+Sof(H3A)+Sof(H3B)+Sof(C4)+Sof(H4A)+Sof(H4B)+Sof(C5)+Sof(C6)+Sof(C7)+
 Sof(H7)+Sof(C8)+Sof(H8)+Sof(C9)+Sof(H9)+Sof(C10)+Sof(C11)+Sof(H11)+Sof(C12)+
 Sof(H12A)+Sof(H12B)+Sof(H12C)+Sof(C13)+Sof(H13A)+Sof(H13B)+Sof(H13C)+Sof(C14)+
 Sof(H14)+Sof(C15)+Sof(H15A)+Sof(H15B)+Sof(H15C)+Sof(C16)+Sof(H16A)+Sof(H16B)+
 Sof(H16C)+Sof(C17)+Sof(C18)+Sof(C19)+Sof(H19)+Sof(C20)+Sof(H20)+Sof(C21)+
 Sof(H21)+Sof(C22)+Sof(C23)+Sof(H23)+Sof(C24)+Sof(H24A)+Sof(H24B)+Sof(H24C)+
 Sof(C25)+Sof(H25A)+Sof(H25B)+Sof(H25C)+Sof(C26)+Sof(H26)+Sof(C27)+Sof(H27A)+
 Sof(H27B)+Sof(H27C)+Sof(C28)+Sof(H28A)+Sof(H28B)+Sof(H28C)+Sof(C29)+Sof(C30)+
 Sof(C31)+Sof(H31)+Sof(C32)+Sof(H32)+Sof(C33)+Sof(H33)+Sof(C34)+Sof(H34)+
 Sof(C35)+Sof(H35)+Sof(C36)+Sof(C37)+Sof(H37)+Sof(C38)+Sof(H38)+Sof(C39)+
 Sof(H39)+Sof(C40)+Sof(H40)+Sof(C41)+Sof(H41)+Sof(C42)+Sof(C43)+Sof(H43)+
 Sof(C44)+Sof(H44)+Sof(C45)+Sof(H45)+Sof(C46)+Sof(H46)+Sof(C47)+Sof(H47)+
 Sof(S1)+Sof(S1A)+Sof(S1B)+Sof(Cu2)+Sof(S2)+Sof(P2)+Sof(N4)+Sof(N5)+Sof(N6)+
 Sof(C48)+Sof(C49)+Sof(H49A)+Sof(H49B)+Sof(C50)+Sof(H50A)+Sof(H50B)+Sof(C51)+
 Sof(H51A)+Sof(H51B)+Sof(C52)+Sof(C53)+Sof(C54)+Sof(H54)+Sof(C55)+Sof(H55)+
 Sof(C56)+Sof(H56)+Sof(C57)+Sof(C58)+Sof(H58)+Sof(C59)+Sof(H59A)+Sof(H59B)+
 Sof(H59C)+Sof(C60)+Sof(H60A)+Sof(H60B)+Sof(H60C)+Sof(C61)+Sof(H61)+Sof(C62)+
 Sof(H62A)+Sof(H62B)+Sof(H62C)+Sof(C63)+Sof(H63A)+Sof(H63B)+Sof(H63C)+Sof(C64)+
 Sof(C65)+Sof(C66)+Sof(H66)+Sof(C67)+Sof(H67)+Sof(C68)+Sof(H68)+Sof(C69)+
 Sof(C70)+Sof(H70)+Sof(C71)+Sof(H71A)+Sof(H71B)+Sof(H71C)+Sof(C72)+Sof(H72A)+
 Sof(H72B)+Sof(H72C)+Sof(C73)+Sof(H73)+Sof(C74)+Sof(H74A)+Sof(H74B)+Sof(H74C)+
 Sof(C75)+Sof(H75A)+Sof(H75B)+Sof(H75C)+Sof(C76)+Sof(C77)+Sof(C78)+Sof(H78)+
 Sof(C79)+Sof(H79)+Sof(C80)+Sof(H80)+Sof(C81)+Sof(H81)+Sof(C82)+Sof(H82)+
 Sof(C83)+Sof(C84)+Sof(H84)+Sof(C85)+Sof(H85)+Sof(C86)+Sof(H86)+Sof(C87)+
 Sof(H87)+Sof(C88)+Sof(H88)+Sof(C89)+Sof(C90)+Sof(H90)+Sof(C91)+Sof(H91)+
 Sof(C92)+Sof(H92)+Sof(C93)+Sof(H93)+Sof(C94)+Sof(H94)+Sof(C1A)+Sof(H1A)+
 Sof(C1B)+Sof(H1B)+Sof(C1C)+Sof(H1C)+Sof(C1D)+Sof(H1D)+Sof(C1E)+Sof(H1E)+
 Sof(C1F)+Sof(H1F)+Sof(C101)+Sof(H101)+Sof(C106)+Sof(H106)+Sof(C105)+Sof(H105)+
 Sof(C104)+Sof(H104)+Sof(C103)+Sof(H103)+Sof(C102)+Sof(H102)+Sof(C95)+Sof(H95)+
 Sof(C96)+Sof(H96)+Sof(C97)+Sof(H97)+Sof(C98)+Sof(H98)+Sof(C99)+Sof(H99)+
 Sof(C100)+Sof(H100)+Sof(Q1)+Sof(Q2)+Sof(Q3)]=1 with esd of 0
 Fixed Sof: S1(0.65) S1A(0.27) S1B(0.08) C1A(0.3) H1A(0.3) C1B(0.3) H1B(0.3)
 C1C(0.3) H1C(0.3) C1D(0.3) H1D(0.3) C1E(0.3) H1E(0.3) C1F(0.3) H1F(0.3)
 C101(0.7) H101(0.7) C106(0.7) H106(0.7) C105(0.7) H105(0.7) C104(0.7)
 H104(0.7) C103(0.7) H103(0.7) C102(0.7) H102(0.7)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C58(H58), C61(H61), C70(H70), C73(H73)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C49(H49A,H49B), C50(H50A,H50B),
 C51(H51A,H51B)
5.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),
  C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C54(H54), C55(H55),
 C56(H56), C66(H66), C67(H67), C68(H68), C78(H78), C79(H79), C80(H80), C81(H81),
  C82(H82), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C90(H90),
 C91(H91), C92(H92), C93(H93), C94(H94), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D),
  C1E(H1E), C1F(H1F), C101(H101), C106(H106), C105(H105), C104(H104),
 C103(H103), C102(H102), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C100(H100)
5.d Fitted hexagon refined as free rotating group:
 C1A(C1B,C1C,C1D,C1E,C1F), C101(C106,C105,C104,C103,C102)
5.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), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C)
;