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_1572669
_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 O, 0.248(C6 H6), 0.752(C5 H12)'
_chemical_formula_sum            'C95.25 H79.51 Cu F2 N2 O'
_chemical_formula_weight         1369.65
_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                86.812(3)
_cell_angle_beta                 83.797(3)
_cell_angle_gamma                63.701(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2312(12)
_cell_length_b                   13.3247(12)
_cell_length_c                   23.320(2)
_cell_measurement_reflns_used    9081
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.38
_cell_measurement_theta_min      2.34
_cell_volume                     3664.1(6)
_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 0.994
_diffrn_measured_fraction_theta_max 0.984
_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  0.0288
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            97364
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.418
_diffrn_reflns_theta_min         1.925
_exptl_absorpt_coefficient_mu    0.355
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6736
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1024 before and 0.0452 after correction.
The Ratio of minimum to maximum transmission is 0.9033.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.607
_exptl_crystal_size_mid          0.434
_exptl_crystal_size_min          0.414
_refine_diff_density_max         1.810
_refine_diff_density_min         -0.763
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     969
_refine_ls_number_reflns         18142
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0542P)^2^+3.4266P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1202
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16644
_reflns_number_total             18142
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba96a_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_database_code               1572669
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.813
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C99-C100 = C99-C98
 1.38 with sigma of 0.02
 C100-C101 = C101-C96 = C96-C97 = C97-C98
 1.39 with sigma of 0.02
 C99-C101 = C99-C97
 2.37 with sigma of 0.04
 C100-C96 = C96-C98
 2.41 with sigma of 0.04
 C101-C97
 2.4 with sigma of 0.04
 C99-C100 \\sim C100-C101 \\sim C101-C96 \\sim C96-C97 \\sim C97-C98 \\sim
C98-C99
 with sigma of 0.02
 C99-C101 \\sim C99-C97 \\sim C101-C97 \\sim C100-C98 \\sim C100-C96 \\sim
C96-C98
 with sigma of 0.04
3. Restrained planarity
 C99, C100, C101, C96, C97, C98
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C99 \\sim C100 \\sim C101 \\sim C96 \\sim C97 \\sim C98: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C99, C100, C101, C96, C97, C98
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C99)=Sof(H99)=Sof(C100)=Sof(H100)=Sof(C101)=Sof(H101)=Sof(C96)=Sof(H96)=
 Sof(C97)=Sof(H97)=Sof(C98)=Sof(H98)=1-FVAR(1)
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C91)=Sof(H91A)=
 Sof(H91B)=Sof(H91C)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=Sof(C94)=Sof(H94A)=
 Sof(H94B)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C24(H24), C57(H57), C43(H43), C10(H10)
7.b Secondary CH2 refined with riding coordinates:
 C93(H93A,H93B), C92(H92A,H92B), C94(H94A,H94B)
7.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C39(H39), C69(H69), C49(H49), C2(H2), C55(H55), C8(H8), C32(H32),
 C59(H59), C16(H16), C65(H65), C3(H3), C48(H48), C51(H51), C6(H6), C63(H63),
 C34(H34), C68(H68), C36(H36), C30(H30), C61(H61), C33(H33), C18(H18), C80(H80),
  C54(H54), C22(H22), C26(H26), C47(H47), C84(H84), C83(H83), C35(H35),
 C45(H45), C66(H66), C19(H19), C90(H90), C62(H62), C67(H67), C21(H21), C12(H12),
  C74(H74), C27(H27), C60(H60), C53(H53), C46(H46), C81(H81), C28(H28),
 C76(H76), C14(H14), C89(H89), C52(H52), C75(H75), C29(H29), C86(H86), C78(H78),
  C15(H15), C13(H13), C77(H77), C20(H20), C87(H87), C99(H99), C100(H100),
 C101(H101), C96(H96), C97(H97), C98(H98)
7.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C23(H23A,H23B,H23C), C91(H91A,H91B,H91C), C95(H95A,H95B,
 H95C)
;
_olex2_submission_special_instructions 'No special instructions were received'