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_1572664
_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         'C75 H55 Cl2 Cu N2, 3(C4 H8 O)'
_chemical_formula_sum            'C87 H79 Cl2 Cu N2 O3'
_chemical_formula_weight         1334.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                88.045(10)
_cell_angle_beta                 89.523(12)
_cell_angle_gamma                84.392(12)
_cell_formula_units_Z            4
_cell_length_a                   14.389(6)
_cell_length_b                   19.498(9)
_cell_length_c                   25.095(11)
_cell_measurement_reflns_used    9990
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.66
_cell_measurement_theta_min      2.17
_cell_volume                     7003(5)
_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 0.998
_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  0.0530
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            344521
_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         25.643
_diffrn_reflns_theta_min         1.887
_exptl_absorpt_coefficient_mu    0.441
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.7125
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0835 before and 0.0578 after correction.
The Ratio of minimum to maximum transmission is 0.9560.
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    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             2808
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.123
_refine_diff_density_max         1.538
_refine_diff_density_min         -0.890
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1711
_refine_ls_number_reflns         26438
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0571P)^2^+12.5581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1375
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23166
_reflns_number_total             26438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba139_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_database_code               1572664
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.902
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C153-C152 = C153-C154
 1.44 with sigma of 0.02
 C152-C151 = O1-C154
 1.53 with sigma of 0.02
 C151-O1
 1.54 with sigma of 0.02
 C153-C151 = C153-O1 = C152-O1 = C151-C154
 2.38 with sigma of 0.04
 C152-C151 \\sim C151-O1 \\sim O1-C154
 with sigma of 0.02
 C153-C152 \\sim C153-C154
 with sigma of 0.02
 C153-C151 \\sim C153-O1
 with sigma of 0.04
 C151-C154 \\sim C152-O1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C153 \\sim C152 \\sim C151 \\sim O1 \\sim C154: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C153, C152, C151, O1, C154
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C55(H55), C23(H23), C85(H85), C10(H10), C42(H42), C98(H98), C117(H117),
 C130(H130)
5.b Secondary CH2 refined with riding coordinates:
 C172(H17C,H17D), C165(H16M,H16N), C173(H17E,H17F), C167(H16A,H16B), C174(H17G,
 H17H), C169(H16C,H16D), C168(H16E,H16F), C171(H17I,H17J), C164(H16O,H16P),
 C161(H16G,H16H), C170(H17A,H17B), C162(H16I,H16J), C160(H16K,H16L), C159(H15A,
 H15B), C163(H16Q,H16R), C157(H15C,H15D), C158(H15E,H15F), C156(H15G,H15H),
 C166(H16S,H16T), C155(H15I,H15J), C153(H15K,H15L), C152(H15M,H15N), C151(H15O,
 H15P), C154(H15Q,H15R)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C77(H77), C38(H38), C40(H40), C78(H78), C83(H83), C8(H8), C2(H2),
 C3(H3), C81(H81), C18(H18), C113(H113), C123(H123), C115(H115), C63(H63),
 C19(H19), C22(H22), C87(H87), C67(H67), C29(H29), C44(H44), C16(H16),
 C119(H119), C12(H12), C142(H142), C106(H106), C91(H91), C110(H110), C48(H48),
 C35(H35), C100(H100), C20(H20), C15(H15), C122(H122), C138(H138), C13(H13),
 C14(H14), C45(H45), C28(H28), C27(H27), C25(H25), C21(H21), C31(H31), C97(H97),
  C89(H89), C26(H26), C57(H57), C88(H88), C108(H108), C93(H93), C66(H66),
 C65(H65), C64(H64), C90(H90), C125(H125), C121(H121), C71(H71), C101(H101),
 C107(H107), C54(H54), C109(H109), C61(H61), C104(H104), C129(H129), C120(H120),
  C141(H141), C32(H32), C46(H46), C33(H33), C75(H75), C96(H96), C34(H34),
 C94(H94), C50(H50), C58(H58), C47(H47), C148(H148), C150(H150), C139(H139),
 C95(H95), C53(H53), C74(H74), C102(H102), C72(H72), C149(H149), C103(H103),
 C136(H136), C59(H59), C128(H128), C146(H146), C140(H140), C60(H60), C147(H147),
  C127(H127), C126(H126), C73(H73), C52(H52), C132(H132), C51(H51), C135(H135),
 C133(H133), C134(H134)
;
_olex2_submission_special_instructions 'No special instructions were received'