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_1572665
_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 O2'
_chemical_formula_sum            'C77 H61 Cu N2 O2'
_chemical_formula_weight         1109.81
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.633(3)
_cell_length_b                   12.0225(12)
_cell_length_c                   14.4644(15)
_cell_measurement_reflns_used    9691
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.50
_cell_measurement_theta_min      2.48
_cell_volume                     5848.7(10)
_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 0.999
_diffrn_measured_fraction_theta_max 0.995
_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  0.0275
_diffrn_reflns_av_unetI/netI     0.0279
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            99750
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.524
_diffrn_reflns_theta_min         1.857
_exptl_absorpt_coefficient_mu    0.425
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6882
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0972 before and 0.0632 after correction.
The Ratio of minimum to maximum transmission is 0.9224.
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    1.260
_exptl_crystal_description       block
_exptl_crystal_F_000             2328
_exptl_crystal_size_max          0.389
_exptl_crystal_size_mid          0.366
_exptl_crystal_size_min          0.347
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.395
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 7717 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0322(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         17342
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0244
_refine_ls_R_factor_gt           0.0239
_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^)+(0.0365P)^2^+0.8858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0654
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.962
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                17012
_reflns_number_total             17342
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba104_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_database_code               1572665
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.852
_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:
 C47(H47), C62(H62), C13(H13), C28(H28)
2.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C11(H11), C43(H43), C82(H82), C64(H64), C32(H32), C45(H45), C9(H9),
 C34(H34), C25(H25), C33(H33), C68(H68), C70(H70), C22(H22), C31(H31), C40(H40),
  C55(H55), C57(H57), C4(H4), C67(H67), C58(H58), C30(H30), C71(H71), C81(H81),
 C19(H19), C5(H5), C24(H24), C72(H72), C66(H66), C79(H79), C80(H80), C74(H74),
 C49(H49), C65(H65), C36(H36), C23(H23), C59(H59), C52(H52), C56(H56), C78(H78),
  C21(H21), C38(H38), C51(H51), C15(H15), C39(H39), C37(H37), C16(H16),
 C18(H18), C17(H17), C50(H50), C73(H73)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C61(H61A,H61B,H61C)
;