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_1564275
_publ_section_title
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 Accelerating the Insertion Reactions of (NHC)Cu-H via Remote Ligand
 Functionalization
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01911B
_journal_year                    2021
_chemical_formula_moiety         '0.5(C134 H102 Cl4 Cu2 N4)'
_chemical_formula_sum            'C67 H51 Cl2 Cu N2'
_chemical_formula_weight         1018.54
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2020-12-29 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.857(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.3769(14)
_cell_length_b                   18.6418(11)
_cell_length_c                   27.6279(19)
_cell_measurement_reflns_used    9570
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.506
_cell_measurement_theta_min      2.493
_cell_volume                     10471.0(12)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_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  0.0574
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            464594
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.537
_diffrn_reflns_theta_min         1.838
_exptl_absorpt_coefficient_mu    0.564
_exptl_absorpt_correction_T_max  0.8253
_exptl_absorpt_correction_T_min  0.7479
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1439 before and 0.0806 after correction.
The Ratio of minimum to maximum transmission is 0.9062.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'orange red'
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_description       block
_exptl_crystal_F_000             4240
_exptl_crystal_size_max          0.422
_exptl_crystal_size_mid          0.409
_exptl_crystal_size_min          0.25
_refine_diff_density_max         3.160
_refine_diff_density_min         -0.957
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1402
_refine_ls_number_reflns         31999
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.1134
_refine_ls_R_factor_gt           0.0960
_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^)+(0.1078P)^2^+31.5716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2558
_refine_ls_wR_factor_ref         0.2713
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25714
_reflns_number_total             31999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           jdeals02_a
_cod_database_code               1564275
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.797
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C5-C10 \\sim C5-C23
 with sigma of 0.02
 C10-C11 \\sim C23-C11
 with sigma of 0.02
 C10-C17 \\sim C23-C24
 with sigma of 0.02
 C19-C21 \\sim C26-C28
 with sigma of 0.04
 C17-C22 \\sim C24-C29
 with sigma of 0.02
 C17-C18 \\sim C24-C25
 with sigma of 0.02
 C137-C136 \\sim C132-C131
 with sigma of 0.02
 C129-C138 \\sim C129-C133
 with sigma of 0.04
 C22-C21 \\sim C29-C28
 with sigma of 0.02
 C18-C19 \\sim C25-C26
 with sigma of 0.02
 C129-C139 \\sim C129-C134
 with sigma of 0.02
 C20-C19 \\sim C27-C26
 with sigma of 0.02
 C20-C21 \\sim C27-C28
 with sigma of 0.02
 C136-C138 \\sim C131-C133
 with sigma of 0.04
 C18-C20 \\sim C25-C27
 with sigma of 0.04
 C5-C17 \\sim C5-C24
 with sigma of 0.04
 C10-C22 \\sim C23-C29
 with sigma of 0.04
 C10-C18 \\sim C23-C25
 with sigma of 0.04
 C129-C135 \\sim C129-C130
 with sigma of 0.02
 C135-C136 \\sim C130-C131
 with sigma of 0.02
 C11-C17 \\sim C11-C24
 with sigma of 0.04
 C137-C138 \\sim C132-C133
 with sigma of 0.02
 C17-C19 \\sim C24-C26
 with sigma of 0.04
 C139-C138 \\sim C134-C133
 with sigma of 0.02
 C17-C21 \\sim C24-C28
 with sigma of 0.04
 C129-C136 \\sim C129-C131
 with sigma of 0.04
 C135-C137 \\sim C130-C132
 with sigma of 0.04
 C137-C139 \\sim C132-C134
 with sigma of 0.04
 C22-C18 \\sim C29-C25
 with sigma of 0.04
 C22-C20 \\sim C29-C27
 with sigma of 0.04
 C116-C118 \\sim C116-C124
 with sigma of 0.04
 C117-C119 \\sim C123-C125
 with sigma of 0.04
 C118-C120 \\sim C124-C126
 with sigma of 0.04
 C119-C120 \\sim C125-C126
 with sigma of 0.02
 C119-C121 \\sim C125-C127
 with sigma of 0.04
 C120-C121 \\sim C126-C127
 with sigma of 0.02
 C116-C122 \\sim C116-C128
 with sigma of 0.04
 C117-C121 \\sim C123-C127
 with sigma of 0.04
 C122-C121 \\sim C128-C127
 with sigma of 0.02
 C118-C122 \\sim C124-C128
 with sigma of 0.04
 C120-C122 \\sim C126-C128
 with sigma of 0.04
 C116-C117 \\sim C116-C123
 with sigma of 0.02
 C117-C118 \\sim C123-C124
 with sigma of 0.02
 C117-C122 \\sim C123-C128
 with sigma of 0.02
 C118-C119 \\sim C124-C125
 with sigma of 0.02
3. Others
 Fixed Sof: C10(0.75) H10(0.75) H116(0.66667) H11A(0.33333) C117(0.75)
 C118(0.75) H118(0.75) C17(0.75) C119(0.75) H119(0.75) C22(0.75) H22(0.75)
 C135(0.5) H135(0.5) C137(0.5) H137(0.5) C18(0.75) H18(0.75) C139(0.5)
 H139(0.5) C20(0.75) H20(0.75) C19(0.75) H19(0.75) C120(0.75) H120(0.75)
 C122(0.75) H122(0.75) C21(0.75) H21(0.75) C136(0.5) H136(0.5) C121(0.75)
 H121(0.75) C138(0.5) H138(0.5) C24(0.25) C25(0.25) H25(0.25) C26(0.25)
 H26(0.25) C27(0.25) H27(0.25) C28(0.25) H28(0.25) C29(0.25) H29(0.25)
 C23(0.25) H23(0.25) C134(0.5) H134(0.5) C133(0.5) H133(0.5) C132(0.5)
 H132(0.5) C131(0.5) H131(0.5) C130(0.5) H130(0.5) C123(0.25) C124(0.25)
 H124(0.25) C125(0.25) H125(0.25) C126(0.25) H126(0.25) C127(0.25) H127(0.25)
 C128(0.25) H128(0.25)
4.a Ternary CH refined with riding coordinates:
 C62(H62), C49(H49), C84(H84), C97(H97), C30(H30), C140(H140), C10(H10),
 C116(H116), C116(H11A), C23(H23)
4.b Aromatic/amide H refined with riding coordinates:
 C77(H77), C76(H76), C2(H2), C45(H45), C82(H82), C47(H47), C3(H3), C8(H8),
 C6(H6), C80(H80), C92(H92), C114(H114), C36(H36), C112(H112), C70(H70),
 C55(H55), C93(H93), C94(H94), C96(H96), C142(H142), C118(H118), C35(H35),
 C71(H71), C87(H87), C86(H86), C42(H42), C68(H68), C95(H95), C12(H12), C88(H88),
  C74(H74), C101(H101), C102(H102), C38(H38), C143(H143), C53(H53), C64(H64),
 C103(H103), C54(H54), C89(H89), C90(H90), C66(H66), C67(H67), C119(H119),
 C99(H99), C52(H52), C146(H146), C51(H51), C65(H65), C41(H41), C72(H72),
 C100(H100), C109(H109), C22(H22), C32(H32), C34(H34), C152(H152), C135(H135),
 C39(H39), C40(H40), C144(H144), C137(H137), C18(H18), C73(H73), C57(H57),
 C148(H148), C139(H139), C20(H20), C105(H105), C16(H16), C13(H13), C19(H19),
 C58(H58), C33(H33), C61(H61), C120(H120), C122(H122), C145(H145), C21(H21),
 C59(H59), C108(H108), C14(H14), C15(H15), C107(H107), C136(H136), C106(H106),
 C60(H60), C121(H121), C138(H138), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C134(H134), C133(H133), C132(H132), C131(H131), C130(H130),
 C124(H124), C125(H125), C126(H126), C127(H127), C128(H128), C151(H151),
 C150(H150), C149(H149)
;
_olex2_submission_special_instructions 'No special instructions were received'