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_1564272
_publ_section_title
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 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
'C75 H68 Cl Cu N2, C0.99 H2 Cl2, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C76.5 H71 Cl4 Cu N2'
_chemical_formula_weight         1223.66
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-14 deposited with the CCDC.	2021-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.687(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2428(15)
_cell_length_b                   11.0690(10)
_cell_length_c                   37.635(4)
_cell_measurement_reflns_used    9461
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      32.59
_cell_measurement_theta_min      2.29
_cell_volume                     6766.0(11)
_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)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            258763
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.617
_diffrn_reflns_theta_min         2.227
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.524
_exptl_absorpt_correction_T_max  0.8019
_exptl_absorpt_correction_T_min  0.7539
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0958 before and 0.0443 after correction.
The Ratio of minimum to maximum transmission is 0.9401.
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    1.201
_exptl_crystal_description       block
_exptl_crystal_F_000             2564
_exptl_crystal_size_max          0.514
_exptl_crystal_size_mid          0.388
_exptl_crystal_size_min          0.298
_refine_diff_density_max         2.680
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.195
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     782
_refine_ls_number_reflns         24653
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.195
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0613
_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^)+(0.0507P)^2^+9.4183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1589
_refine_ls_wR_factor_ref         0.1599
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23521
_reflns_number_total             24653
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01911b3.cif
_cod_data_source_block           jdebt05_a
_cod_original_formula_sum        'C76.50 H71 Cl4 Cu N2'
_cod_database_code               1564272
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.860
_shelx_estimated_absorpt_t_min   0.775
_olex2_refinement_description
;
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
 Cl5-C77 \\sim Cl6-C77
 with sigma of 0.02
3. Others
 Fixed Sof: Cl5(0.7) Cl3(0.5) Cl2(0.5) H77A(0.7) H77B(0.7) H77C(0.3) H77D(0.3)
 C76(0.5) H76A(0.5) H76B(0.5) Cl6(0.3)
4.a Ternary CH refined with riding coordinates:
 C63(H63), C27(H27), C10(H10), C46(H46)
4.b Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B), C77(H77C,H77D), C76(H76A,H76B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C3(H3), C75(H75), C42(H42), C33(H33), C69(H69), C44(H44),
 C65(H65), C6(H6), C32(H32), C66(H66), C71(H71), C68(H68), C39(H39), C67(H67),
 C16(H16), C58(H58), C52(H52), C29(H29), C35(H35), C12(H12), C48(H48), C31(H31),
  C38(H38), C18(H18), C13(H13), C74(H74), C22(H22), C37(H37), C14(H14),
 C15(H15), C19(H19), C54(H54), C55(H55), C30(H30), C36(H36), C56(H56), C49(H49),
  C50(H50), C73(H73), C57(H57), C20(H20), C72(H72), C21(H21), C51(H51)
4.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C61(H61A,H61B,
 H61C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'