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_7719117
_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         'C60 H48 Cu P4, 2(B0.05 F0.4), 2(B0.45 F1.6)'
_chemical_formula_sum            'C60 H48 B Cu F4 P4'
_chemical_formula_weight         1043.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/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                 100.5352(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.55747(10)
_cell_length_b                   12.57977(9)
_cell_length_c                   14.98164(10)
_cell_measurement_reflns_used    40234
_cell_measurement_temperature    153
_cell_measurement_theta_max      76.3230
_cell_measurement_theta_min      2.9350
_cell_volume                     2512.04(3)
_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 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -87.00  -5.00   0.50    0.05    --  -48.77 113.00 -19.00  164
  2  \w    -37.00  24.00   0.50    0.05    --  -48.77  37.00 -90.00  122
  3  \w    -14.00  25.00   0.50    0.05    --  -48.77  19.00-120.00   78
  4  \w    -14.00  25.00   0.50    0.05    --  -48.77  19.00 -60.00   78
  5  \w    -61.00  23.00   0.50    0.05    --  -48.77  57.00 -60.00  168
  6  \w    -65.00 -30.00   0.50    0.05    -- -102.00  57.00-180.00   70
  7  \w    -65.00 -30.00   0.50    0.05    -- -102.00  57.00-120.00   70
  8  \w    -65.00 -30.00   0.50    0.05    -- -102.00  57.00 -60.00   70
  9  \w    -65.00 -30.00   0.50    0.05    -- -102.00  57.00   0.00   70
 10  \w    -65.00 -30.00   0.50    0.05    -- -102.00  57.00  30.00   70
 11  \w   -108.00 -30.00   0.50    0.05    -- -102.00 113.00 -19.00  156
 12  \w   -107.00 -30.00   0.50    0.05    -- -102.00 104.00  27.23  154
 13  \w   -111.00 -30.00   0.50    0.05    -- -102.00 125.00 150.00  162
 14  \w   -107.00 -30.00   0.50    0.05    -- -102.00 106.00  88.36  154
 15  \w   -121.00 -66.00   0.50    0.05    --  -48.77 -77.00 -30.00  110
 16  \w   -121.00 -74.00   0.50    0.05    --  -48.77-125.00   0.00   94
 17  \w   -121.00 -74.00   0.50    0.05    --  -48.77-125.00  30.00   94
 18  \w      9.00  88.00   0.50    0.05    --   48.77-113.00-111.00  158
 19  \w     31.00 108.00   0.50    0.05    --  102.75-113.00-111.00  154
 20  \w     31.00  69.00   0.50    0.05    --  102.75 -57.00 -60.00   76
 21  \w     31.00 106.00   0.50    0.05    --  102.75 -99.00 -60.00  150
 22  \w     31.00 111.00   0.50    0.05    --  102.75-125.00-180.00  160
 23  \w     31.00 106.00   0.50    0.05    --  102.75 -99.00 -90.00  150
 24  \w     31.00  69.00   0.50    0.05    --  102.75 -57.00 -30.00   76
 25  \w     31.00 106.00   0.50    0.05    --  102.75 -99.00   0.00  150
 26  \w     31.00 106.00   0.50    0.05    --  102.75 -99.00-120.00  150
 27  \w     31.00  69.00   0.50    0.05    --  102.75 -57.00  60.00   76
 28  \w     31.00 111.00   0.50    0.05    --  102.75-125.00  90.00  160
 29  \w     95.00 174.00   0.50    0.05    --  102.75  37.00  90.00  158
 30  \w     86.00 174.00   0.50    0.05    --  102.75 113.00 -19.00  176
 31  \w     36.00 121.00   0.50    0.05    --   48.77  57.00-180.00  170
 32  \w    -24.00  18.00   0.50    0.05    --   48.77 -19.00-120.00   84
 33  \w    -23.00  41.00   0.50    0.05    --   48.77 -37.00  30.00  128
 34  \w   -174.00 -82.00   0.50    0.05    -- -102.00-113.00-111.00  184
 35  \w   -174.00 -92.00   0.50    0.05    -- -102.00 -49.00 -19.84  164
 36  \w   -174.00 -83.00   0.50    0.05    -- -102.00 -73.00 110.68  182
 37  \w   -174.00 -90.00   0.50    0.05    -- -102.00 -55.00 165.43  168
 38  \w   -174.00 -94.00   0.50    0.05    -- -102.00 -37.00  60.00  160
 39  \w   -174.00 -94.00   0.50    0.05    -- -102.00 -37.00 -90.00  160
;
_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      0.1020267000
_diffrn_orient_matrix_UB_12      0.0500439000
_diffrn_orient_matrix_UB_13      0.0408215000
_diffrn_orient_matrix_UB_21      0.0389093000
_diffrn_orient_matrix_UB_22      -0.1095755000
_diffrn_orient_matrix_UB_23      0.0367100000
_diffrn_orient_matrix_UB_31      0.0379573000
_diffrn_orient_matrix_UB_32      -0.0222295000
_diffrn_orient_matrix_UB_33      -0.0889804000
_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  0.0323
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            46518
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.311
_diffrn_reflns_theta_min         3.513
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.265
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50055
_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    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             1076
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.00091(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         5203
_refine_ls_number_restraints     241
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0362P)^2^+1.4675P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0735
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5050
_reflns_number_total             5203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01099c2.cif
_cod_data_source_block           Cudppbz2BF4
_cod_depositor_comments
'Adding full bibliography for 7719116--7719120.cif.'
_cod_database_code               7719117
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H P Cu B F'
_cell_oxdiff_angle_alpha         89.9936(8)
_cell_oxdiff_angle_beta          100.5634(8)
_cell_oxdiff_angle_gamma         89.9953(8)
_cell_oxdiff_length_a            13.55602(12)
_cell_oxdiff_length_b            12.57640(12)
_cell_oxdiff_length_c            14.98863(15)
_cell_oxdiff_measurement_reflns_used 40234
_cell_oxdiff_volume              2512.04(4)
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.660
_olex2_refinement_description
;
1. Restrained distances
 F00I-F00Z \\sim F00I-F010 \\sim F00I-F1 \\sim F00Z-F010 \\sim F00Z-F1 \\sim
F010-F1
 with sigma of 0.02
 B011-F00I \\sim B011-F00Z \\sim B011-F010 \\sim B011-F1
 with sigma of 0.01
 F00I-B011 \\sim F2-B0
 with sigma of 0.02
 F00Z-B011 \\sim F3-B0
 with sigma of 0.02
 F010-B011 \\sim F0-B0
 with sigma of 0.02
 B011-F1 \\sim B0-F1A
 with sigma of 0.02
 F00I-F00Z \\sim F2-F3
 with sigma of 0.04
 F00I-F010 \\sim F2-F0
 with sigma of 0.04
 F00I-F1 \\sim F2-F1A
 with sigma of 0.04
 F00Z-F010 \\sim F3-F0
 with sigma of 0.04
 F00Z-F1 \\sim F3-F1A
 with sigma of 0.04
 F010-F1 \\sim F0-F1A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
F00I \\sim B011 \\sim F00Z \\sim F010 \\sim F1 \\sim F0 \\sim B0 \\sim F2 \\sim
F1A \\sim F3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
3. Rigid body (RIGU) restrains
 B011, F00I, F1, F010, F00Z
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
 F1A, B0, F2, F0, F3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: F00I(0.1) F00Z(0.1) F010(0.1) B011(0.05) F1(0.1) B0(0.45) F2(0.4)
 F1A(0.4) F0(0.4) F3(0.4)
5.a Aromatic/amide H refined with riding coordinates:
 C004(H004), C009(H009), C00C(H00C), C00D(H00D), C00E(H00E), C00F(H00F),
 C00G(H00G), C00H(H00H), C00J(H00J), C00K(H00K), C00L(H00L), C00M(H00M),
 C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S),
 C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y)
;
_shelx_res_checksum              82556
_shelx_hkl_checksum              69853
_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 1.549
_oxdiff_exptl_absorpt_empirical_full_min 0.583