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_1572672
_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         '4(C104 H74 Cu2 P4), 4(C6 H6), 2[C6H12]'
_chemical_formula_sum            'C452 H344 Cu8 P16'
_chemical_formula_weight         6779.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-03-25
_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                 90.423(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   13.6127(7)
_cell_length_b                   24.0012(10)
_cell_length_c                   26.5094(14)
_cell_measurement_reflns_used    9216
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.724
_cell_measurement_theta_min      2.263
_cell_volume                     8660.9(7)
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            222111
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.742
_diffrn_reflns_theta_min         2.137
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.7062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1016 before and 0.0644 after correction. The Ratio of minimum to maximum transmission is 0.9475. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             3528
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.107
_refine_diff_density_max         0.563
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 14504 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0207(17)
_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     2096
_refine_ls_number_reflns         33010
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0292
_refine_ls_shift/su_max          0.033
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0414P)^2^+3.1515P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0742
_refine_ls_wR_factor_ref         0.0752
_reflns_Friedel_coverage         0.947
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                31509
_reflns_number_total             33010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02982h3.cif
_cod_data_source_block           ba145b_final_a
_cod_depositor_comments
'Adding full bibliography for 1572662--1572672.cif.'
_cod_database_code               1572672
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 P8-C187 \\sim P8-C1A
 with sigma of 0.02
 C187-C192 \\sim C1A-C1F
 with sigma of 0.02
 C187-C188 \\sim C1A-C1B
 with sigma of 0.02
 C192-C191 \\sim C1F-C1E
 with sigma of 0.02
 C191-C1D \\sim C1E-C190
 with sigma of 0.02
 C1D-C189 \\sim C190-C1C
 with sigma of 0.02
 C188-C189 \\sim C1B-C1C
 with sigma of 0.02
 P8-C192 \\sim P8-C1F
 with sigma of 0.04
 P8-C188 \\sim P8-C1B
 with sigma of 0.04
 C187-C191 \\sim C1A-C1E
 with sigma of 0.04
 C187-C189 \\sim C1A-C1C
 with sigma of 0.04
 C192-C1D \\sim C1F-C190
 with sigma of 0.04
 C192-C188 \\sim C1F-C1B
 with sigma of 0.04
 C191-C189 \\sim C1E-C1C
 with sigma of 0.04
 C1D-C188 \\sim C190-C1B
 with sigma of 0.04
 C194-C195 \\sim C194-C1G
 with sigma of 0.02
 C195-C200 \\sim C1G-C1H
 with sigma of 0.02
 C195-C196 \\sim C1G-C1L
 with sigma of 0.02
 C199-C200 \\sim C1I-C1H
 with sigma of 0.02
 C199-C198 \\sim C1I-C1J
 with sigma of 0.02
 C196-C197 \\sim C1L-C1K
 with sigma of 0.02
 C197-C198 \\sim C1K-C1J
 with sigma of 0.02
 C194-C200 \\sim C194-C1H
 with sigma of 0.04
 C194-C196 \\sim C194-C1L
 with sigma of 0.04
 C195-C199 \\sim C1G-C1I
 with sigma of 0.04
 C195-C197 \\sim C1G-C1K
 with sigma of 0.04
 C199-C197 \\sim C1I-C1K
 with sigma of 0.04
 C200-C196 \\sim C1H-C1L
 with sigma of 0.04
 C200-C198 \\sim C1H-C1J
 with sigma of 0.04
 C196-C198 \\sim C1L-C1J
 with sigma of 0.04
 C201-C04V \\sim C201-C202
 with sigma of 0.02
 C04V-C05V \\sim C202-C203
 with sigma of 0.02
 C05V-C2AA \\sim C203-C204
 with sigma of 0.02
 C05V-C236 \\sim C203-C208
 with sigma of 0.02
 C2AA-C1AA \\sim C204-C205
 with sigma of 0.02
 C1AA-C0AA \\sim C205-C206
 with sigma of 0.02
 C0AA-C237 \\sim C206-C207
 with sigma of 0.02
 C237-C236 \\sim C207-C208
 with sigma of 0.02
 C201-C05V \\sim C201-C203
 with sigma of 0.04
 C04V-C2AA \\sim C202-C204
 with sigma of 0.04
 C04V-C236 \\sim C202-C208
 with sigma of 0.04
 C05V-C1AA \\sim C203-C205
 with sigma of 0.04
 C05V-C237 \\sim C203-C207
 with sigma of 0.04
 C2AA-C0AA \\sim C204-C206
 with sigma of 0.04
 C2AA-C236 \\sim C204-C208
 with sigma of 0.04
 C1AA-C237 \\sim C205-C207
 with sigma of 0.04
 C0AA-C236 \\sim C206-C208
 with sigma of 0.04
3. Others
 Sof(C1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=Sof(C1E)=
 Sof(H1E)=Sof(C1F)=Sof(H1F)=1-FVAR(1)
 Sof(C187)=Sof(C188)=Sof(H188)=Sof(C189)=Sof(H189)=Sof(C190)=Sof(H190)=
 Sof(C191)=Sof(H191)=Sof(C192)=Sof(H192)=FVAR(1)
 Sof(C1G)=Sof(C1L)=Sof(H1L)=Sof(C1K)=Sof(H1K)=Sof(C1J)=Sof(H1J)=Sof(C1I)=
 Sof(H1I)=Sof(C1H)=Sof(H1H)=1-FVAR(2)
 Sof(C195)=Sof(C196)=Sof(H196)=Sof(C197)=Sof(H197)=Sof(C198)=Sof(H198)=
 Sof(C199)=Sof(H199)=Sof(C200)=Sof(H200)=FVAR(2)
 Sof(C202)=Sof(C203)=Sof(C204)=Sof(H204)=Sof(C205)=Sof(H205)=Sof(C206)=
 Sof(H206)=Sof(C207)=Sof(H207)=Sof(C208)=Sof(H208)=1-FVAR(3)
 Sof(C04V)=Sof(C05V)=Sof(C2AA)=Sof(H2AA)=Sof(C1AA)=Sof(H1AA)=Sof(C0AA)=
 Sof(H0AA)=Sof(C237)=Sof(H237)=Sof(C236)=Sof(H236)=FVAR(3)
4.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C40(H40), C8(H8), C25(H25), C144(H144), C44(H44),
 C52(H52), C112(H112), C54(H54), C160(H160), C9(H9), C88(H88), C12(H12),
 C186(H186), C152(H152), C142(H142), C124(H124), C162(H162), C41(H41), C43(H43),
  C150(H150), C58(H58), C6(H6), C47(H47), C42(H42), C48(H48), C49(H49),
 C153(H153), C36(H36), C114(H114), C75(H75), C19(H19), C20(H20), C38(H38),
 C118(H118), C106(H106), C135(H135), C87(H87), C53(H53), C26(H26), C63(H63),
 C69(H69), C129(H129), C173(H173), C17(H17), C134(H134), C113(H113), C56(H56),
 C2(H2), C156(H156), C64(H64), C179(H179), C62(H62), C50(H50), C168(H168),
 C140(H140), C148(H148), C46(H46), C78(H78), C145(H145), C31(H31), C55(H55),
 C121(H121), C157(H157), C132(H132), C119(H119), C18(H18), C141(H141),
 C131(H131), C116(H116), C84(H84), C151(H151), C5(H5), C167(H167), C107(H107),
 C59(H59), C159(H159), C30(H30), C86(H86), C123(H123), C82(H82), C81(H81),
 C104(H104), C163(H163), C100(H100), C61(H61), C122(H122), C146(H146),
 C138(H138), C185(H185), C74(H74), C11(H11), C178(H178), C154(H154), C182(H182),
  C188(H188), C189(H189), C190(H190), C191(H191), C192(H192), C214(H214),
 C37(H37), C101(H101), C34(H34), C4(H4), C108(H108), C96(H96), C80(H80),
 C115(H115), C28(H28), C219(H219), C85(H85), C27(H27), C130(H130), C110(H110),
 C10(H10), C147(H147), C79(H79), C70(H70), C158(H158), C3(H3), C109(H109),
 C103(H103), C174(H174), C72(H72), C35(H35), C165(H165), C175(H175), C102(H102),
  C176(H176), C139(H139), C166(H166), C218(H218), C220(H220), C209(H209),
 C211(H211), C95(H95), C184(H184), C213(H213), C71(H71), C210(H210), C212(H212),
  C2AA(H2AA), C1AA(H1AA), C0AA(H0AA), C237(H237), C236(H236), C183(H183),
 C92(H92), C217(H217), C94(H94), C216(H216), C215(H215), C93(H93), C1B(H1B),
 C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C196(H196), C197(H197), C198(H198),
 C199(H199), C200(H200), C1L(H1L), C1K(H1K), C1J(H1J), C1I(H1I), C1H(H1H),
 C204(H204), C205(H205), C206(H206), C207(H207), C208(H208)
4.b Fitted hexagon refined as free rotating group:
 C187(C188,C189,C190,C191,C192), C05V(C2AA,C1AA,C0AA,C237,C236), C1A(C1B,C1C,
 C1D,C1E,C1F), C195(C196,C197,C198,C199,C200), C1G(C1L,C1K,C1J,C1I,C1H),
 C203(C204,C205,C206,C207,C208)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 112 electrons were 
found in a volume of 726\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
2[C6H12] per formula unit 
which account for 96 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2