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_1572671
_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
'C88 H63 Cl2 Cu F2 N2 O, 0.209(C6 H6), 0.791(C5 H12)'
_chemical_formula_sum            'C93.21 H73.75 Cl2 Cu F2 N2 O'
_chemical_formula_weight         1410.24
_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                86.485(2)
_cell_angle_beta                 83.009(2)
_cell_angle_gamma                63.633(2)
_cell_formula_units_Z            2
_cell_length_a                   13.2620(8)
_cell_length_b                   13.3089(8)
_cell_length_c                   23.2168(14)
_cell_measurement_reflns_used    9678
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.27
_cell_measurement_theta_min      2.67
_cell_volume                     3644.1(4)
_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 0.998
_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  0.0409
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            208704
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.329
_diffrn_reflns_theta_min         1.917
_exptl_absorpt_coefficient_mu    0.430
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1278 before and 0.0536 after correction.
The Ratio of minimum to maximum transmission is 0.9209.
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    1.285
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.443
_exptl_crystal_size_min          0.162
_refine_diff_density_max         1.447
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     967
_refine_ls_number_reflns         18131
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0411P)^2^+3.0596P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0992
_refine_ls_wR_factor_ref         0.1009
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17069
_reflns_number_total             18131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba108a_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_database_code               1572671
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.820
_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
 C106-C107 = C106-C105
 1.38 with sigma of 0.02
 C107-C108 = C108-C103 = C103-C104 = C104-C105
 1.39 with sigma of 0.02
 C106-C108 = C106-C104
 2.37 with sigma of 0.04
 C107-C103 = C103-C105
 2.41 with sigma of 0.04
 C108-C104
 2.4 with sigma of 0.04
 C106-C107 \\sim C107-C108 \\sim C108-C103 \\sim C103-C104 \\sim C104-C105
\\sim C105-C106
 with sigma of 0.02
 C106-C108 \\sim C106-C104 \\sim C108-C104 \\sim C107-C105 \\sim C107-C103
\\sim C103-C105
 with sigma of 0.04
3. Restrained planarity
 C106, C107, C108, C103, C104, C105
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C106 \\sim C107 \\sim C108 \\sim C103 \\sim C104 \\sim C105: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C106, C107, C108, C103, C104, C105
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C106)=Sof(H106)=Sof(C107)=Sof(H107)=Sof(C108)=Sof(H108)=Sof(C103)=
 Sof(H103)=Sof(C104)=Sof(H104)=Sof(C105)=Sof(H105)=1-FVAR(1)
 Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(C102)=Sof(H10C)=Sof(H10D)=Sof(H10E)=
 Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=Sof(C101)=Sof(H10F)=Sof(H10G)=Sof(C99)=
 Sof(H99A)=Sof(H99B)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C46(H46), C73(H73), C60(H60), C27(H27)
7.b Secondary CH2 refined with riding coordinates:
 C100(H10A,H10B), C101(H10F,H10G), C99(H99A,H99B)
7.c Aromatic/amide H refined with riding coordinates:
 C44(H44), C42(H42), C52(H52), C20(H20), C24(H24), C54(H54), C62(H62), C9(H9),
 C48(H48), C58(H58), C66(H66), C11(H11), C70(H70), C72(H72), C4(H4), C33(H33),
 C57(H57), C68(H68), C21(H21), C5(H5), C39(H39), C29(H29), C19(H19), C77(H77),
 C56(H56), C50(H50), C71(H71), C65(H65), C49(H49), C55(H55), C35(H35), C51(H51),
  C22(H22), C15(H15), C93(H93), C78(H78), C87(H87), C69(H69), C81(H81),
 C23(H23), C88(H88), C63(H63), C30(H30), C36(H36), C95(H95), C84(H84), C94(H94),
  C80(H80), C85(H85), C31(H31), C64(H64), C32(H32), C38(H38), C37(H37),
 C97(H97), C96(H96), C18(H18), C16(H16), C17(H17), C106(H106), C107(H107),
 C108(H108), C103(H103), C104(H104), C105(H105)
7.d Idealised Me refined as rotating group:
 C102(H10C,H10D,H10E), C98(H98A,H98B,H98C)
;