Metal ligand cooperativity in the direct carboxylation and esterification of terminal alkynes by Cu-CNC complexes bearing 2,6-lutidine linkers.
Back, Nick; Guthrie, Emylie; Zhu, Chengxu; de Visser, Sam P.; Tahsini, Laleh; Chemical science 17 (2026) 2087–2101; doi:10.1039/d5sc08379f

data_1576739
_publ_section_title
;
 Metal ligand cooperativity in the direct carboxylation and esterification
 of terminal alkynes by Cu-CNC complexes bearing 2,6-lutidine linkers.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              2087
_journal_page_last               2101
_journal_paper_doi               10.1039/d5sc08379f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C37 H45 Cu N5, F6 P, C2 H3 N'
_chemical_formula_sum            'C39 H48 Cu F6 N6 P'
_chemical_formula_weight         809.34
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-09 deposited with the CCDC.	2026-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.337(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0022(4)
_cell_length_b                   15.0039(5)
_cell_length_c                   23.1511(8)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.120
_cell_measurement_theta_min      2.224
_cell_volume                     3815.2(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  'XL  (Sheldrick, 2008)'
_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 1.000
_diffrn_measurement_device_type  'Bruker D8 Venture Duo with Photon 3'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0705
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            125754
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         2.006
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7107
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0770 before and 0.0666 after correction.
The Ratio of minimum to maximum transmission is 0.9526.
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    1.409
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.186
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         9463
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0300
_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^)+(0.0271P)^2^+2.8972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0753
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8232
_reflns_number_total             9463
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08379f2.cif
_cod_data_source_block           tah23_07
_cod_database_code               1576739
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.867
_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. Uiso/Uaniso restraints and constraints
C32 \\sim C33B \\sim C33A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 C33B, C33A, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H32A)=Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(H32)=Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), C32(H32), C32(H32A), C35(H35)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C10(H10A,H10B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C16(H16),
 C17(H17), C18(H18), C28(H28), C29(H29), C30(H30)
5.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C33A(H33A,H33B,H33C), C33B(H33D,H33E,H33F), C34(H34A,H34B,H34C),
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              87126
_olex2_exptl_crystal_mounting_method 'MiTeGen 100 micron MicroLoop'
_olex2_submission_special_instructions 'No special instructions were received'