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_1564267
_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         'C75 H69 Cu N2, C7 H8'
_chemical_formula_sum            'C82 H77 Cu N2'
_chemical_formula_weight         1153.99
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-12-22
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2020-12-31 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
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_cell_angle_alpha                90
_cell_angle_beta                 99.399(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4302(8)
_cell_length_b                   18.0856(8)
_cell_length_c                   21.8382(10)
_cell_measurement_reflns_used    9270
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      29.996
_cell_measurement_theta_min      2.376
_cell_volume                     6402.1(5)
_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 0.999
_diffrn_measured_fraction_theta_max 1.000
_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  0.0760
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            367691
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.032
_diffrn_reflns_theta_min         2.032
_exptl_absorpt_coefficient_mu    0.388
_exptl_absorpt_correction_T_max  0.9196
_exptl_absorpt_correction_T_min  0.8074
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1191 before and 0.0642 after correction.
The Ratio of minimum to maximum transmission is 0.8780.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.197
_exptl_crystal_description       plate
_exptl_crystal_F_000             2448
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.302
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.455
_refine_diff_density_min         -0.482
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 11899 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.202(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1557
_refine_ls_number_reflns         37439
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0771
_refine_ls_R_factor_gt           0.0556
_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^)+(0.0610P)^2^+4.2008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1308
_refine_ls_wR_factor_ref         0.1417
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                29874
_reflns_number_total             37439
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           jdeals03_b
_cod_database_code               1564267
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C70-C71 \\sim C70-C72
 with sigma of 0.02
 C71-C73 \\sim C72-C74
 with sigma of 0.02
 C76-C73 \\sim C76-C74
 with sigma of 0.04
 C70-C73 \\sim C70-C74
 with sigma of 0.04
3. Others
 Fixed Sof: H70A(0.5) H70B(0.5) H70C(0.5) H70D(0.5) H75A(0.5) H75B(0.5)
 H75C(0.5) H75D(0.5) C71(0.5) H71A(0.5) H71B(0.5) C73(0.5) H73A(0.5) H73B(0.5)
 C72(0.5) H72A(0.5) H72B(0.5) C74(0.5) H74A(0.5) H74B(0.5)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C24(H24), C43(H43), C57(H57), C87(H87), C101(H101), C120(H120),
 C134(H134)
4.b Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C70(H70C,H70D), C75(H75A,H75B), C75(H75C,H75D), C76(H76A,
 H76B), C71(H71A,H71B), C73(H73A,H73B), C72(H72A,H72B), C74(H74A,H74B),
 C147(H14A,H14B), C148(H14C,H14D), C149(H14E,H14F), C150(H15A,H15B), C152(H15C,
 H15D)
4.c 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),
  C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65), C66(H66),
 C67(H67), C68(H68), C69(H69), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55),
  C79(H79), C80(H80), C83(H83), C85(H85), C89(H89), C90(H90), C91(H91),
 C92(H92), C93(H93), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C103(H103), C104(H104), C105(H105), C106(H106), C107(H107), C109(H109),
 C110(H110), C111(H111), C112(H112), C113(H113), C116(H116), C118(H118),
 C122(H122), C123(H123), C124(H124), C125(H125), C126(H126), C128(H128),
 C129(H129), C130(H130), C131(H131), C132(H132), C136(H136), C137(H137),
 C138(H138), C139(H139), C140(H140), C142(H142), C143(H143), C144(H144),
 C145(H145), C146(H146), C157(H157), C158(H158), C159(H159), C160(H160),
 C161(H161), C164(H164), C165(H165), C166(H166), C167(H167), C168(H168)
4.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C56(H56A,H56B,H56C), C77(H77A,H77B,H77C), C100(H10A,H10B,
 H10C), C133(H13A,H13B,H13C), C154(H15E,H15F,H15G), C162(H16A,H16B,H16C),
 C169(H16D,H16E,H16F)
;