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_1572666
_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         'C90 H69 Cu F2 N2 O3'
_chemical_formula_sum            'C90 H69 Cu F2 N2 O3'
_chemical_formula_weight         1328.01
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.6667(15)
_cell_length_b                   23.566(2)
_cell_length_c                   34.121(3)
_cell_measurement_reflns_used    9433
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.30
_cell_measurement_theta_min      2.30
_cell_volume                     14206(2)
_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  0.0618
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            209088
_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         28.349
_diffrn_reflns_theta_min         2.101
_exptl_absorpt_coefficient_mu    0.366
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1354 before and 0.0636 after correction.
The Ratio of minimum to maximum transmission is 0.7838.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_description       block
_exptl_crystal_F_000             5552
_exptl_crystal_size_max          0.581
_exptl_crystal_size_mid          0.427
_exptl_crystal_size_min          0.172
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         17721
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0292P)^2^+14.6534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1031
_refine_ls_wR_factor_ref         0.1129
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14176
_reflns_number_total             17721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba103_final2_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_original_cell_volume        14205(2)
_cod_database_code               1572666
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.816
_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. Restrained distances
 O4-C40 \\sim O3-C40
 with sigma of 0.02
 O4-C57 \\sim O3-C56
 with sigma of 0.02
 C57-H57A \\sim C56-H56A
 with sigma of 0.02
 C57-H57B \\sim C56-H56B
 with sigma of 0.02
 C57-H57C \\sim C56-H56C
 with sigma of 0.02
 O4-H57A \\sim O3-H56A
 with sigma of 0.04
 O4-H57B \\sim O3-H56B
 with sigma of 0.04
 O4-H57C \\sim O3-H56C
 with sigma of 0.04
 C40-C57 \\sim C40-C56
 with sigma of 0.04
 H57A-H57B \\sim H56A-H56B
 with sigma of 0.04
 H57A-H57C \\sim H56A-H56C
 with sigma of 0.04
 H57B-H57C \\sim H56B-H56C
 with sigma of 0.04
 C84-C85 \\sim C84-C92
 with sigma of 0.02
 C85-C86 \\sim C92-C93
 with sigma of 0.02
 C86-C87 \\sim C93-C98
 with sigma of 0.02
 C86-C91 \\sim C93-C94
 with sigma of 0.02
 C87-C88 \\sim C98-C97
 with sigma of 0.02
 C89-C88 \\sim C96-C97
 with sigma of 0.02
 C89-C90 \\sim C96-C95
 with sigma of 0.02
 C90-C91 \\sim C95-C94
 with sigma of 0.02
 C84-C86 \\sim C84-C93
 with sigma of 0.04
 C85-C87 \\sim C92-C98
 with sigma of 0.04
 C85-C91 \\sim C92-C94
 with sigma of 0.04
 C86-C88 \\sim C93-C97
 with sigma of 0.04
 C86-C90 \\sim C93-C95
 with sigma of 0.04
 C87-C89 \\sim C98-C96
 with sigma of 0.04
 C87-C91 \\sim C98-C94
 with sigma of 0.04
 C89-C91 \\sim C96-C94
 with sigma of 0.04
 C88-C90 \\sim C97-C95
 with sigma of 0.04
3. Others
 Sof(O3)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=1-FVAR(1)
 Sof(O4)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=FVAR(1)
 Sof(C92)=Sof(C93)=Sof(C98)=Sof(H98)=Sof(C97)=Sof(H97)=Sof(C96)=Sof(H96)=
 Sof(C95)=Sof(H95)=Sof(C94)=Sof(H94)=1-FVAR(2)
 Sof(C85)=Sof(C86)=Sof(C87)=Sof(H87)=Sof(C89)=Sof(H89)=Sof(C88)=Sof(H88)=
 Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C58(H58), C43(H43), C10(H10)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C8(H8), C6(H6), C70(H70), C26(H26), C67(H67), C32(H32),
 C66(H66), C36(H36), C34(H34), C18(H18), C83(H83), C35(H35), C39(H39), C33(H33),
  C12(H12), C22(H22), C73(H73), C16(H16), C64(H64), C69(H69), C41(H41),
 C77(H77), C68(H68), C27(H27), C79(H79), C60(H60), C15(H15), C29(H29), C62(H62),
  C63(H63), C74(H74), C82(H82), C28(H28), C51(H51), C30(H30), C13(H13),
 C14(H14), C45(H45), C61(H61), C76(H76), C49(H49), C80(H80), C55(H55), C21(H21),
  C19(H19), C53(H53), C20(H20), C46(H46), C47(H47), C52(H52), C54(H54),
 C48(H48), C87(H87), C89(H89), C88(H88), C90(H90), C91(H91), C98(H98), C97(H97),
  C96(H96), C95(H95), C94(H94)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C57(H57A,H57B,H57C), C56(H56A,H56B,H56C)
;
_olex2_submission_special_instructions 'No special instructions were received'