Homoleptic copper(I)-bisphosphine complexes as photoredox catalysts.
Saha, Priya; Tomita, Ryunosuke; Tsuneda, Takao; Jiang, Pingyu; Taketsugu, Tetsuya; Jin, Mingoo; Huang, Dennis Chung-Yang; Dalton transactions (Cambridge, England : 2003) 54 (2025) 11725–11731; doi:10.1039/d5dt01099c

data_7719116
_publ_section_title
;
 Homoleptic copper(I)-bisphosphine complexes as photoredox catalysts.
;
_journal_issue                   30
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11725
_journal_page_last               11731
_journal_paper_doi               10.1039/d5dt01099c
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C72 H56 Cu P4, B F4, 1[C3H6O]'
_chemical_formula_sum            'C75 H62 B Cu F4 O P4'
_chemical_formula_weight         1253.47
_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             2025-07-04
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-04 deposited with the CCDC.	2025-07-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.1530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.19330(10)
_cell_length_b                   22.87440(10)
_cell_length_c                   20.81190(10)
_cell_measurement_reflns_used    83812
_cell_measurement_temperature    153
_cell_measurement_theta_max      76.2590
_cell_measurement_theta_min      2.8550
_cell_volume                     6182.44(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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      153
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -66.00  24.00   0.50    0.57    --  -48.41  71.00 116.00  180
  2  \w    -14.00  25.00   0.50    0.57    --  -48.41  19.00  30.00   78
  3  \w    -14.00  25.00   0.50    0.57    --  -48.41  19.00  90.00   78
  4  \w    -14.00  25.00   0.50    0.57    --  -48.41  19.00 -30.00   78
  5  \w    -14.00  25.00   0.50    0.57    --  -48.41  19.00 -90.00   78
  6  \w    -65.00 -30.00   0.50    0.57    -- -102.00  57.00  60.00   70
  7  \w    -65.00 -30.00   0.50    0.57    -- -102.00  57.00  90.00   70
  8  \w    -95.00 -30.00   0.50    0.57    -- -102.00  71.00 116.00  130
  9  \w   -119.00 -30.00   0.50    0.57    --  -48.41 -71.00 -14.00  178
 10  \w   -119.00 -74.00   0.50    0.57    --  -48.41-125.00  60.00   90
 11  \w   -119.00 -74.00   0.50    0.57    --  -48.41-125.00 150.00   90
 12  \w    -22.00  67.00   0.50    0.57    --   48.41 -71.00 -14.00  178
 13  \w     31.00  99.00   0.50    0.57    --  102.75 -71.00 -14.00  136
 14  \w     31.00  69.00   0.50    0.57    --  102.75 -57.00  90.00   76
 15  \w     34.00  66.00   0.50    0.57    --  102.75 -57.00  60.00   64
 16  \w     35.00 103.00   0.50    0.57    --  102.75 -99.00   0.00  136
 17  \w     33.00 113.00   0.50    0.57    --  102.75 -77.00 -90.00  160
 18  \w     41.00 120.00   0.50    0.57    --   48.41  37.00-150.00  158
 19  \w    102.00 174.00   0.50    0.57    --  102.75  57.00 -90.00  144
 20  \w    113.00 171.00   0.50    0.57    --  102.75  77.00   0.00  116
 21  \w    138.00 171.00   0.50    0.57    --  102.75  77.00  90.00   66
 22  \w    103.00 156.00   0.50    0.57    --  102.75  37.00  60.00  106
 23  \w     95.00 175.00   0.50    0.57    --  102.75  19.00 120.00  160
 24  \w     95.00 169.00   0.50    0.57    --  102.75  37.00  30.00  148
 25  \w     97.00 123.00   0.50    0.57    --  102.75  77.00  90.00   52
 26  \w     85.00 174.00   0.50    0.57    --  102.75  71.00 116.00  178
 27  \w     82.00 174.00   0.50    0.57    --  102.75  77.00  30.00  184
 28  \w     90.00 174.00   0.50    0.57    --  102.75  57.00-120.00  168
 29  \w     30.00 119.00   0.50    0.57    --   48.41  71.00 116.00  178
 30  \w     31.00  69.00   0.50    0.57    --  102.75 -57.00 120.00   76
 31  \w     33.00 101.00   0.50    0.57    --  102.75 -99.00  60.00  136
 32  \w     31.00  68.00   0.50    0.57    --  102.75 -57.00 -90.00   74
 33  \w     39.00  65.00   0.50    0.57    --  102.75 -57.00-150.00   52
 34  \w     31.00  69.00   0.50    0.57    --  102.75 -57.00-180.00   76
 35  \w    -24.00  18.00   0.50    0.57    --   48.41 -19.00  90.00   84
 36  \w    -22.00  61.00   0.50    0.57    --   48.41 -57.00 120.00  166
 37  \w   -174.00 -84.00   0.50    0.57    -- -102.00 -71.00 -14.00  180
 38  \w   -175.00 -94.00   0.50    0.57    -- -102.00 -19.00-150.00  162
 39  \w   -174.00 -89.00   0.50    0.57    -- -102.00 -57.00-120.00  170
 40  \w   -174.00 -89.00   0.50    0.57    -- -102.00 -57.00-150.00  170
 41  \w   -175.00 -94.00   0.50    0.57    -- -102.00 -19.00-120.00  162
 42  \w   -175.00 -94.00   0.50    0.57    -- -102.00 -19.00-180.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0986715000
_diffrn_orient_matrix_UB_12      0.0338413000
_diffrn_orient_matrix_UB_13      -0.0064643000
_diffrn_orient_matrix_UB_21      -0.0182498000
_diffrn_orient_matrix_UB_22      0.0415844000
_diffrn_orient_matrix_UB_23      0.0550747000
_diffrn_orient_matrix_UB_31      0.0633278000
_diffrn_orient_matrix_UB_32      -0.0407265000
_diffrn_orient_matrix_UB_33      0.0508013000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0371
_diffrn_reflns_av_unetI/netI     0.0162
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            116259
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.353
_diffrn_reflns_theta_min         3.695
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.948
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             2600
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.708
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     785
_refine_ls_number_reflns         12787
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0387
_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^)+(0.0604P)^2^+3.8189P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1055
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12232
_reflns_number_total             12787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01099c2.cif
_cod_data_source_block           CuBIPHEP2BF4
_cod_depositor_comments
'Adding full bibliography for 7719116--7719120.cif.'
_cod_database_code               7719116
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu C H P B F'
_cell_oxdiff_angle_alpha         90.0276(6)
_cell_oxdiff_angle_beta          100.1606(6)
_cell_oxdiff_angle_gamma         90.0032(6)
_cell_oxdiff_length_a            13.19015(11)
_cell_oxdiff_length_b            22.88123(17)
_cell_oxdiff_length_c            20.81124(15)
_cell_oxdiff_measurement_reflns_used 83812
_cell_oxdiff_volume              6182.47(8)
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.759
_olex2_refinement_description
;
1. Restrained distances
 F006-B02A \\sim F1-B02B
 with sigma of 0.02
 F007-B02A \\sim F0-B02B
 with sigma of 0.02
 F013-B02A \\sim F2-B02B
 with sigma of 0.02
 F01H-B02A \\sim F01I-B02B
 with sigma of 0.02
 F006-F007 \\sim F1-F0
 with sigma of 0.04
 F006-F013 \\sim F1-F2
 with sigma of 0.04
 F006-F01H \\sim F1-F01I
 with sigma of 0.04
 F007-F013 \\sim F0-F2
 with sigma of 0.04
 F007-F01H \\sim F0-F01I
 with sigma of 0.04
 F013-F01H \\sim F2-F01I
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
F006 \\sim F007 \\sim F013 \\sim F01H \\sim B02A \\sim F0 \\sim F1 \\sim F2
\\sim F01I \\sim B02B: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
3. Others
 Sof(F0)=Sof(F1)=Sof(F2)=Sof(F01I)=Sof(B02B)=1-FVAR(1)
 Sof(F006)=Sof(F007)=Sof(F013)=Sof(F01H)=Sof(B02A)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00I(H00I), C00K(H00K), C00M(H00M), C00N(H00N),
 C00P(H00P), C00R(H00R), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W),
 C00X(H00X), C00Y(H00Y), C00Z(H00Z), C012(H012), C014(H014), C015(H015),
 C016(H016), C017(H017), C018(H018), C019(H019), C01A(H01A), C01B(H01B),
 C01C(H01C), C01D(H01D), C01E(H01E), C01G(H01G), C01I(H01I), C01J(H01J),
 C01K(H01K), C01L(H01L), C01M(H01M), C01N(H01N), C01O(H01O), C01P(H01P),
 C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T), C01U(H01U), C01V(H01V),
 C01W(H01W), C01X(H01X), C01Y(H01Y), C01Z(H01Z), C020(H020), C021(H021),
 C022(H022), C023(H023), C024(H024), C025(H025), C026(H026), C027(H027),
 C028(H028), C029(H029)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 108 electrons were 
found in a volume of 794\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[C3H6O] per Asymmetric Unit 
which account for 128 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              98725
_shelx_hkl_checksum              176
_shelx_fab_checksum              647
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.822
_oxdiff_exptl_absorpt_empirical_full_min 0.651