Accelerating the Insertion Reactions of (NHC)Cu-H via Remote Ligand Functionalization
Speelman, Amy L.; Tran, Ba; Erickson, Jeremy D.; Vasiliu, Monica; Dixon, David A.; Bullock, R. Morris; Chemical Science  (2021) –; doi:10.1039/D1SC01911B

data_1564268
_publ_section_title
;
 Accelerating the Insertion Reactions of (NHC)Cu-H via Remote Ligand
 Functionalization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01911B
_journal_year                    2021
_chemical_formula_moiety         'C138 H114 Cu2 N4 O4'
_chemical_formula_sum            'C138 H114 Cu2 N4 O4'
_chemical_formula_weight         2019.41
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-12 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.815(4)
_cell_length_b                   27.671(3)
_cell_length_c                   29.647(4)
_cell_measurement_reflns_used    9937
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.465
_cell_measurement_theta_min      2.434
_cell_volume                     21998(5)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1092
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            1982883
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.626
_diffrn_reflns_theta_min         2.152
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.445
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1337 before and 0.0665 after correction. The Ratio of minimum to maximum transmission is 0.9260. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             8480
_exptl_crystal_size_max          0.358
_exptl_crystal_size_mid          0.335
_exptl_crystal_size_min          0.252
_refine_diff_density_max         0.825
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1752
_refine_ls_number_reflns         40141
_refine_ls_number_restraints     110
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0649
_refine_ls_R_factor_gt           0.0462
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0456P)^2^+15.3770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1192
_reflns_Friedel_coverage         0.000
_reflns_number_gt                31382
_reflns_number_total             40141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           als_1_138
_cod_database_code               1564268
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.857
_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
 C127-C128 \\sim C127-C1D
 with sigma of 0.02
 C127-C134 \\sim C127-C1B
 with sigma of 0.02
 C128-C129 \\sim C1D-C1E
 with sigma of 0.02
 C129-C130 \\sim C1E-C130
 with sigma of 0.02
 C130-C132 \\sim C130-C1C
 with sigma of 0.02
 C132-C134 \\sim C1C-C1B
 with sigma of 0.02
 C127-C129 \\sim C127-C1E
 with sigma of 0.04
 C127-C132 \\sim C127-C1C
 with sigma of 0.04
 C128-C130 \\sim C1D-C130
 with sigma of 0.04
 C130-C134 \\sim C130-C1B
 with sigma of 0.04
 C20-C21 \\sim C20-C21A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C21-C26 \\sim C21A-C26A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C20-C22 \\sim C20-C22A
 with sigma of 0.04
 C20-C26 \\sim C20-C26A
 with sigma of 0.04
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C21-C25 \\sim C21A-C25A
 with sigma of 0.04
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C22-C26 \\sim C22A-C26A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C76-C77 \\sim C76-C77A
 with sigma of 0.02
 C76-C81 \\sim C76-C81A
 with sigma of 0.02
 C77-C78 \\sim C77A-C78A
 with sigma of 0.02
 C78-C79 \\sim C78A-C79
 with sigma of 0.02
 C79-C80 \\sim C79-C80A
 with sigma of 0.02
 C80-C81 \\sim C80A-C81A
 with sigma of 0.02
 C76-C78 \\sim C76-C78A
 with sigma of 0.04
 C76-C80 \\sim C76-C80A
 with sigma of 0.04
 C77-C79 \\sim C77A-C79
 with sigma of 0.04
 C79-C81 \\sim C79-C81A
 with sigma of 0.04
 C4AA-C5AA \\sim C4AA-C5AB
 with sigma of 0.02
 C4AA-C8AA \\sim C4AA-C3BA
 with sigma of 0.02
 C5AA-C3AA \\sim C5AB-C3AB
 with sigma of 0.02
 C3AA-C6AA \\sim C3AB-C1BA
 with sigma of 0.02
 C6AA-C7AA \\sim C1BA-C2BA
 with sigma of 0.02
 C7AA-C8AA \\sim C2BA-C3BA
 with sigma of 0.02
 C4AA-C3AA \\sim C4AA-C3AB
 with sigma of 0.04
 C4AA-C7AA \\sim C4AA-C2BA
 with sigma of 0.04
 C5AA-C6AA \\sim C5AB-C1BA
 with sigma of 0.04
 C3AA-C7AA \\sim C3AB-C2BA
 with sigma of 0.04
 C6AA-C8AA \\sim C1BA-C3BA
 with sigma of 0.04
 O3-C0BA \\sim O3A-C0BA
 with sigma of 0.02
 O3-C5 \\sim O3A-C5A
 with sigma of 0.02
 C0BA-C5 \\sim C0BA-C5A
 with sigma of 0.04
 C61-C62 \\sim C61-C62A
 with sigma of 0.02
 C61-C66 \\sim C61-C66A
 with sigma of 0.02
 C62-C63 \\sim C62A-C63A
 with sigma of 0.02
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 C64-C65 \\sim C64A-C65A
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A
 with sigma of 0.02
 C61-C63 \\sim C61-C63A
 with sigma of 0.04
 C61-C65 \\sim C61-C65A
 with sigma of 0.04
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C63-C65 \\sim C63A-C65A
 with sigma of 0.04
 C64-C66 \\sim C64A-C66A
 with sigma of 0.04
 C37-C38 \\sim C37-C38A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 C38-C43 \\sim C38A-C43A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 C42-C43 \\sim C42A-C43A
 with sigma of 0.02
 C37-C39 \\sim C37-C39A
 with sigma of 0.04
 C37-C43 \\sim C37-C43A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 C38-C42 \\sim C38A-C42A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 C39-C43 \\sim C39A-C43A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.04
 C41-C43 \\sim C41A-C43A
 with sigma of 0.04
 O12-C71 \\sim O12A-C71
 with sigma of 0.02
 O12-C72 \\sim O12A-C72A
 with sigma of 0.02
 C71-C72 \\sim C71-C72A
 with sigma of 0.04
 C37-C44 \\sim C37-C44A
 with sigma of 0.02
 C44-C45 \\sim C44A-C45A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C37-C45 \\sim C37-C45A
 with sigma of 0.04
 C44-C46 \\sim C44A-C46A
 with sigma of 0.04
 C44-C48 \\sim C44A-C48A
 with sigma of 0.04
 C45-C47 \\sim C45A-C47A
 with sigma of 0.04
 C46-C48 \\sim C46A-C48A
 with sigma of 0.04
 C120-C121 \\sim C120-C1L
 with sigma of 0.02
 C121-C122 \\sim C1L-C1Q
 with sigma of 0.02
 C121-C126 \\sim C1L-C1M
 with sigma of 0.02
 C122-C123 \\sim C1Q-C1P
 with sigma of 0.02
 C123-C124 \\sim C1P-C1O
 with sigma of 0.02
 C124-C125 \\sim C1O-C1N
 with sigma of 0.02
 C125-C126 \\sim C1N-C1M
 with sigma of 0.02
 C120-C122 \\sim C120-C1Q
 with sigma of 0.04
 C120-C126 \\sim C120-C1M
 with sigma of 0.04
 C121-C123 \\sim C1L-C1P
 with sigma of 0.04
 C121-C125 \\sim C1L-C1N
 with sigma of 0.04
 C122-C124 \\sim C1Q-C1O
 with sigma of 0.04
 C122-C126 \\sim C1Q-C1M
 with sigma of 0.04
 C123-C125 \\sim C1P-C1N
 with sigma of 0.04
 C124-C126 \\sim C1O-C1M
 with sigma of 0.04
 C82-C83 \\sim C82-C83A
 with sigma of 0.02
 C82-C87 \\sim C82-C87A
 with sigma of 0.02
 C83-C84 \\sim C83A-C84A
 with sigma of 0.02
 C84-C85 \\sim C84A-C85A
 with sigma of 0.02
 C85-C86 \\sim C85A-C86A
 with sigma of 0.02
 C86-C87 \\sim C86A-C87A
 with sigma of 0.02
 C82-C84 \\sim C82-C84A
 with sigma of 0.04
 C82-C86 \\sim C82-C86A
 with sigma of 0.04
 C83-C85 \\sim C83A-C85A
 with sigma of 0.04
 C84-C86 \\sim C84A-C86A
 with sigma of 0.04
 C85-C87 \\sim C85A-C87A
 with sigma of 0.04
3. Others
 Fixed Sof: O3(0.25) O12(0.8) C5(0.25) H5A(0.25) H5B(0.25) H5C(0.25)
 H2AA(0.85) H2AB(0.15) C4AA(0.85) C5AA(0.85) H5AA(0.85) C3AA(0.85) H3AA(0.85)
 C6AA(0.85) H6AA(0.85) C7AA(0.85) H7AA(0.85) C8AA(0.85) H8AA(0.85) H20(0.6)
 H20A(0.4) C21(0.6) C22(0.6) H22(0.6) C23(0.6) H23(0.6) C24(0.6) H24(0.6)
 C25(0.6) H25(0.6) C26(0.6) H26(0.6) H37(0.5) H37A(0.5) C38(0.5) C39(0.5)
 H39(0.5) C40(0.5) H40(0.5) C41(0.5) H41(0.5) C42(0.5) H42(0.5) C43(0.5)
 H43(0.5) C44(0.5) C45(0.5) H45(0.5) C46(0.5) H46(0.5) C47(0.5) H47(0.5)
 C48(0.5) H48(0.5) H49(0.6) H49A(0.4) C62(0.5) H62(0.5) C63(0.5) H63(0.5)
 C64(0.5) H64(0.5) C65(0.5) H65(0.5) C66(0.5) H66(0.5) C72(0.8) H72A(0.8)
 H72B(0.8) H72C(0.8) C81A(0.25) H81A(0.25) C80A(0.25) H80A(0.25) H79(0.75)
 H79A(0.25) C78A(0.25) H78A(0.25) C77A(0.25) H77A(0.25) C77(0.75) H77(0.75)
 C78(0.75) H78(0.75) C80(0.75) H80(0.75) C81(0.75) H81(0.75) C83(0.6) H83(0.6)
 C84(0.6) H84(0.6) C85(0.6) H85(0.6) C86(0.6) H86(0.6) C87(0.6) H87(0.6)
 H120(0.8) H12A(0.2) C121(0.8) C122(0.8) H122(0.8) C123(0.8) H123(0.8)
 C124(0.8) H124(0.8) C125(0.8) H125(0.8) C126(0.8) H126(0.8) C128(0.6)
 H128(0.6) C129(0.6) H129(0.6) H130(0.6) H13A(0.4) C132(0.6) H132(0.6)
 C134(0.6) H134(0.6) C1B(0.4) H1B(0.4) C1C(0.4) H1C(0.4) C1D(0.4) H1D(0.4)
 C1E(0.4) H1E(0.4) C21A(0.4) C26A(0.4) H26A(0.4) C25A(0.4) H25A(0.4) C24A(0.4)
 H24A(0.4) C23A(0.4) H23A(0.4) C22A(0.4) H22A(0.4) C4AC(0.15) C3BA(0.15)
 H3BA(0.15) C2BA(0.15) H2BA(0.15) C1BA(0.15) H1BA(0.15) C3AB(0.15) H3AB(0.15)
 C5AB(0.15) H5AB(0.15) O3A(0.75) C5A(0.75) H5AC(0.75) H5AD(0.75) H5AE(0.75)
 C62A(0.5) H62A(0.5) C66A(0.5) H66A(0.5) C65A(0.5) H65A(0.5) C64A(0.5)
 H64A(0.5) C63A(0.5) H63A(0.5) C38A(0.5) C39A(0.5) H39A(0.5) C40A(0.5)
 H40A(0.5) C41A(0.5) H41A(0.5) C42A(0.5) H42A(0.5) C43A(0.5) H43A(0.5)
 O12A(0.2) C72A(0.2) H72D(0.2) H72E(0.2) H72F(0.2) C44A(0.5) C45A(0.5)
 H45A(0.5) C46A(0.5) H46A(0.5) C47A(0.5) H47A(0.5) C48A(0.5) H48A(0.5) C1L(0.2)
 C1M(0.2) H1M(0.2) C1N(0.2) H1N(0.2) C1O(0.2) H1O(0.2) C1P(0.2) H1P(0.2)
 C1Q(0.2) H1Q(0.2) C87A(0.4) H87A(0.4) C86A(0.4) H86A(0.4) C85A(0.4) H85A(0.4)
 C84A(0.4) H84A(0.4) C83A(0.4) H83A(0.4)
4.a Ternary CH refined with riding coordinates:
 C2AA(H2AA), C2AA(H2AB), C20(H20), C20(H20A), C37(H37), C37(H37A), C54(H54),
 C75(H75), C88(H88), C107(H107), C120(H120), C120(H12A)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C9(H9), C10(H10), C3(H3), C5AA(H5AA), C3AA(H3AA), C6AA(H6AA),
 C7AA(H7AA), C8AA(H8AA), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30),
  C31(H31), C32(H32), C33(H33), C34(H34), C39(H39), C40(H40), C41(H41),
 C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
 C49(H49A), C50(H50), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60),
 C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C70(H70), C73(H73),
 C81A(H81A), C80A(H80A), C79(H79), C79(H79A), C78A(H78A), C77A(H77A), C77(H77),
 C78(H78), C80(H80), C81(H81), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87),
  C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C96(H96), C97(H97),
 C98(H98), C99(H99), C100(H100), C102(H102), C105(H105), C109(H109), C110(H110),
  C111(H111), C112(H112), C113(H113), C115(H115), C116(H116), C117(H117),
 C118(H118), C119(H119), C122(H122), C123(H123), C124(H124), C125(H125),
 C126(H126), C128(H128), C129(H129), C130(H130), C130(H13A), C132(H132),
 C134(H134), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E), C26A(H26A), C25A(H25A),
 C24A(H24A), C23A(H23A), C22A(H22A), C3BA(H3BA), C2BA(H2BA), C1BA(H1BA),
 C3AB(H3AB), C5AB(H5AB), C62A(H62A), C66A(H66A), C65A(H65A), C64A(H64A),
 C63A(H63A), C39A(H39A), C40A(H40A), C41A(H41A), C42A(H42A), C43A(H43A),
 C45A(H45A), C46A(H46A), C47A(H47A), C48A(H48A), C1M(H1M), C1N(H1N), C1O(H1O),
 C1P(H1P), C1Q(H1Q), C87A(H87A), C86A(H86A), C85A(H85A), C84A(H84A), C83A(H83A)
4.c Fitted hexagon refined as free rotating group:
 C76(C81A,C80A,C79,C78A,C77A), C4AC(C3BA,C2BA,C1BA,C3AB,C5AB)
4.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C52(H52A,H52B,H52C), C72(H72A,H72B,H72C), C104(H10A,H10B,
 H10C), C5A(H5AC,H5AD,H5AE), C72A(H72D,H72E,H72F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2