Direct observation of β-alkynyl eliminations from unstrained propargylic alkoxide Cu(i) complexes by C-C bond cleavage.
Tran, Ba L.; Fuller, 3rd, Jack T; Erickson, Jeremy D.; Ginovska, Bojana; Raugei, Simone; Chemical science 15 (2024) 17481–17489; doi:10.1039/d4sc02982h

data_1572662
_publ_section_title
;
 Direct observation of &#x3b2;-alkynyl eliminations from unstrained
 propargylic alkoxide Cu(i) complexes by C-C bond cleavage.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              17481
_journal_page_last               17489
_journal_paper_doi               10.1039/d4sc02982h
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C77 H61 Cu N2'
_chemical_formula_sum            'C77 H61 Cu N2'
_chemical_formula_weight         1077.81
_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             2024-03-06
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-04 deposited with the CCDC.	2024-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.731(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1755(13)
_cell_length_b                   29.096(3)
_cell_length_c                   18.610(2)
_cell_measurement_reflns_used    9955
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.50
_cell_measurement_theta_min      2.27
_cell_volume                     5824.6(11)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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  0.0433
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            164915
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.538
_diffrn_reflns_theta_min         1.893
_exptl_absorpt_coefficient_mu    0.422
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6925
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0793 before and 0.0514 after correction.
The Ratio of minimum to maximum transmission is 0.9282.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       block
_exptl_crystal_F_000             2264
_exptl_crystal_size_max          0.311
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.166
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.509
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     723
_refine_ls_number_reflns         17721
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0415
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0497P)^2^+3.7317P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1054
_refine_ls_wR_factor_ref         0.1140
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15129
_reflns_number_total             17721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba102_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_original_cell_volume        5824.4(12)
_cod_database_code               1572662
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C24(H24), C10(H10), C43(H43), C57(H57)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C3(H3), C41(H41), C2(H2), C32(H32), C22(H22), C59(H59),
 C39(H39), C21(H21), C63(H63), C20(H20), C33(H33), C55(H55), C36(H36), C30(H30),
  C18(H18), C12(H12), C19(H19), C65(H65), C34(H34), C69(H69), C45(H45),
 C51(H51), C67(H67), C35(H35), C66(H66), C26(H26), C60(H60), C54(H54), C27(H27),
  C62(H62), C77(H77), C68(H68), C49(H49), C61(H61), C73(H73), C52(H52),
 C53(H53), C76(H76), C13(H13), C75(H75), C16(H16), C48(H48), C14(H14), C47(H47),
  C28(H28), C29(H29), C15(H15), C46(H46), C74(H74)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C56(H56A,H56B,H56C)
;