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_1564266
_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_absolute_configuration ad
_chemical_formula_moiety         'C69 H56 Cl Cu N2 O2'
_chemical_formula_sum            'C69 H56 Cl Cu N2 O2'
_chemical_formula_weight         1044.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-09-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2020-12-14 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.940(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4801(7)
_cell_length_b                   18.5079(9)
_cell_length_c                   20.3673(11)
_cell_measurement_reflns_used    9040
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.47
_cell_measurement_theta_min      2.42
_cell_volume                     5455.2(5)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0457
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            213006
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.543
_diffrn_reflns_theta_min         2.001
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.498
_exptl_absorpt_correction_T_max  0.8749
_exptl_absorpt_correction_T_min  0.7835
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1209 before and 0.0633 after correction.
The Ratio of minimum to maximum transmission is 0.8955.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             2184
_exptl_crystal_size_max          0.332
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.922
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 10420 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.024(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1527
_refine_ls_number_reflns         32727
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0430P)^2^+2.1562P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0957
_refine_ls_wR_factor_ref         0.1039
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                26470
_reflns_number_total             32727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           jdebt03
_cod_database_code               1564266
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.852
_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
 C112-C119 \\sim C112-C1A
 with sigma of 0.02
 C119-C120 \\sim C1A-C1F
 with sigma of 0.02
 C119-C124 \\sim C1A-C1B
 with sigma of 0.02
 C120-C121 \\sim C1F-C1E
 with sigma of 0.02
 C121-C122 \\sim C1E-C1D
 with sigma of 0.02
 C122-C123 \\sim C1D-C1C
 with sigma of 0.02
 C123-C124 \\sim C1C-C1B
 with sigma of 0.02
 C112-C120 \\sim C112-C1F
 with sigma of 0.04
 C112-C124 \\sim C112-C1B
 with sigma of 0.04
 C119-C121 \\sim C1A-C1E
 with sigma of 0.04
 C119-C123 \\sim C1A-C1C
 with sigma of 0.04
 C120-C122 \\sim C1F-C1D
 with sigma of 0.04
 C120-C124 \\sim C1F-C1B
 with sigma of 0.04
 C121-C123 \\sim C1E-C1C
 with sigma of 0.04
 C122-C124 \\sim C1D-C1B
 with sigma of 0.04
 C107-C112 \\sim C107-C1G
 with sigma of 0.02
 C112-C113 \\sim C1G-C113
 with sigma of 0.02
 C112-C119 \\sim C1G-C119
 with sigma of 0.02
 C112-C1A \\sim C1G-C1A
 with sigma of 0.02
 C106-C107 \\sim C106-C1L
 with sigma of 0.02
 C107-C108 \\sim C1L-C1J
 with sigma of 0.02
 C107-C112 \\sim C1L-C112
 with sigma of 0.02
 C107-C1G \\sim C1L-C1G
 with sigma of 0.02
 C108-C109 \\sim C1J-C1I
 with sigma of 0.02
 C109-O4 \\sim C1I-O4A
 with sigma of 0.02
 C109-C110 \\sim C1I-C1K
 with sigma of 0.02
 O4-C125 \\sim O4A-C1H
 with sigma of 0.02
 C110-C111 \\sim C1K-C111
 with sigma of 0.02
 C106-C108 \\sim C106-C1J
 with sigma of 0.04
 C107-C109 \\sim C1L-C1I
 with sigma of 0.04
 C108-O4 \\sim C1J-O4A
 with sigma of 0.04
 C108-C110 \\sim C1J-C1K
 with sigma of 0.04
 C108-C112 \\sim C1J-C112
 with sigma of 0.04
 C108-C1G \\sim C1J-C1G
 with sigma of 0.04
 C109-C125 \\sim C1I-C1H
 with sigma of 0.04
 C109-C111 \\sim C1I-C111
 with sigma of 0.04
 O4-C110 \\sim O4A-C1K
 with sigma of 0.04
 C93-C94 \\sim C93-C94A
 with sigma of 0.02
 C94-C95 \\sim C94A-C95A
 with sigma of 0.02
 C94-C99 \\sim C94A-C99A
 with sigma of 0.02
 C95-C96 \\sim C95A-C96A
 with sigma of 0.02
 C96-C97 \\sim C96A-C97
 with sigma of 0.02
 C97-C98 \\sim C97-C98A
 with sigma of 0.02
 C98-C99 \\sim C98A-C99A
 with sigma of 0.02
 C93-C95 \\sim C93-C95A
 with sigma of 0.04
 C93-C99 \\sim C93-C99A
 with sigma of 0.04
 C94-C96 \\sim C94A-C96A
 with sigma of 0.04
 C94-C98 \\sim C94A-C98A
 with sigma of 0.04
 C95-C97 \\sim C95A-C97
 with sigma of 0.04
 C95-C99 \\sim C95A-C99A
 with sigma of 0.04
 C97-C99 \\sim C97-C99A
 with sigma of 0.04
3. Others
 Fixed Sof: H93(0.6) H93A(0.4) O4(0.6667) C94(0.6) C95(0.6) H95(0.6) C96(0.6)
 H96(0.6) C97(0.6) H97(0.6) C98(0.6) H98(0.6) C99(0.6) H99(0.6) C107(0.6667)
 C108(0.6667) H108(0.6667) C109(0.6667) C110(0.6667) H110(0.6667) C112(0.6667)
 H112(0.6667) C119(0.6667) C120(0.6667) H120(0.6667) C121(0.6667) H121(0.6667)
 C122(0.6667) H122(0.6667) C123(0.6667) H123(0.6667) C124(0.6667) H124(0.6667)
 C125(0.6667) H12A(0.6667) H12B(0.6667) H12C(0.6667) O4A(0.3333) C1A(0.3333)
 C1B(0.3333) H1B(0.3333) C1C(0.3333) H1C(0.3333) C1D(0.3333) H1D(0.3333)
 C1E(0.3333) H1E(0.3333) C1F(0.3333) H1F(0.3333) C1G(0.3333) H1G(0.3333)
 C1H(0.3333) H1HA(0.3333) H1HB(0.3333) H1HC(0.3333) C1I(0.3333) C1J(0.3333)
 H1J(0.3333) C1K(0.3333) H1K(0.3333) C1L(0.3333) C94A(0.4) C95A(0.4) H95A(0.4)
 C96A(0.4) H96A(0.4) C97A(0.4) H97A(0.4) C98A(0.4) H98A(0.4) C99A(0.4) H99A(0.4)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C24(H24), C43(H43), C57(H57), C79(H79), C93(H93), C93(H93A),
 C126(H126), C112(H112), C1G(H1G)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C39(H39), C41(H41), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
  C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C59(H59), C60(H60),
 C61(H61), C62(H62), C63(H63), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69),
  C71(H71), C72(H72), C75(H75), C77(H77), C81(H81), C82(H82), C83(H83),
 C84(H84), C85(H85), C87(H87), C88(H88), C89(H89), C90(H90), C91(H91),
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), C114(H114),
 C115(H115), C116(H116), C117(H117), C118(H118), C128(H128), C129(H129),
 C130(H130), C131(H131), C132(H132), C134(H134), C135(H135), C136(H136),
 C137(H137), C138(H138), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C108(H108), C110(H110), C120(H120), C121(H121), C122(H122), C123(H123),
 C124(H124), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1J(H1J),
 C1K(H1K), C95A(H95A), C96A(H96A), C97A(H97A), C98A(H98A), C99A(H99A)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C56(H56A,H56B,H56C), C92(H92A,H92B,H92C), C125(H12A,H12B,
 H12C), C1H(H1HA,H1HB,H1HC)
;