Structural and reactivity investigations using organo-copper(i) and zinc(ii) complexes with hydrogen and carbon dioxide.
Cowie, Bradley E.; Phanopoulos, Andreas; Shaffer, Milo S. P.; Williams, Charlotte K.; Chemical science 17 (2026) 564–578; doi:10.1039/d5sc05666g

data_1576716
_publ_section_title
;
 Structural and reactivity investigations using organo-copper(i) and
 zinc(ii) complexes with hydrogen and carbon dioxide.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              564
_journal_page_last               578
_journal_paper_doi               10.1039/d5sc05666g
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C75 H63 Cu3 P6, C7 H8'
_chemical_formula_sum            'C82 H71 Cu3 P6'
_chemical_formula_weight         1432.82
_chemical_name_common            028bec23
_chemical_name_systematic        '[Cu3(dppm_prime)3]'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Light-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             2023-05-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-12 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.8081(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.83010(4)
_cell_length_b                   23.24282(6)
_cell_length_c                   23.96377(7)
_cell_measurement_reflns_used    129373
_cell_measurement_temperature    150.01(14)
_cell_measurement_theta_max      76.1200
_cell_measurement_theta_min      3.3830
_cell_volume                     7540.16(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (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_environment      N~2~
_diffrn_ambient_temperature      150.01(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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      1.00  32.00   1.00    1.00    --  -42.66  19.00  60.00   31
  2  \w     -3.00  28.00   1.00    1.00    --  -42.66  19.00 -90.00   31
  3  \w     -3.00  23.00   1.00    1.00    --  -42.66  19.00 150.00   26
  4  \w     -5.00  36.00   1.00    1.00    --  -42.66  19.00-150.00   41
  5  \w     -5.00  35.00   1.00    1.00    --  -42.66  19.00   0.00   40
  6  \w     61.00 129.00   1.00    1.00    --   42.66 178.00-180.00   68
  7  \w     68.00 109.00   1.00    1.00    --   42.66 178.00  30.00   41
  8  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00  60.00   25
  9  \w    105.00 173.00   1.00    4.00    --  111.00  77.00 120.00   68
 10  \w     42.00  94.00   1.00    4.00    --  111.00 -77.00-150.00   52
 11  \w     41.00  67.00   1.00    4.00    --  111.00 -45.00 -30.00   26
 12  \w     44.00  69.00   1.00    4.00    --  111.00 -45.00 120.00   25
 13  \w     44.00 107.00   1.00    4.00    --  111.00-120.00   2.00   63
 14  \w     30.00  61.00   1.00    4.00    --  111.00 -95.00 150.00   31
 15  \w     44.00  70.00   1.00    4.00    --  111.00-125.00 -30.00   26
 16  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00 150.00   25
 17  \w     66.00 101.00   1.00    4.00    --  111.00 -95.00  60.00   35
 18  \w     36.00  62.00   1.00    4.00    --  111.00 -95.00  60.00   26
 19  \w    109.00 175.00   1.00    4.00    --  111.00  77.00   0.00   66
 20  \w     77.00 102.00   1.00    4.00    --  111.00-125.00 -30.00   25
 21  \w     91.00 177.00   1.00    4.00    --  111.00  30.00 -90.00   86
 22  \w     74.00 100.00   1.00    4.00    --  111.00 -95.00 150.00   26
 23  \w     78.00 107.00   1.00    4.00    --  111.00-108.00  38.79   29
 24  \w     62.00  88.00   1.00    4.00    --  111.00 -61.00-120.00   26
 25  \w     46.00  88.00   1.00    4.00    --  111.00-125.00-120.00   42
 26  \w     72.00 111.00   1.00    4.00    --  111.00-125.00 150.00   39
 27  \w    102.00 127.00   1.00    4.00    --  111.00-144.00 131.07   25
 28  \w   -110.00 -53.00   1.00    1.00    --  -42.66 178.00 -60.00   57
 29  \w     -5.00  34.00   1.00    1.00    --  -42.66  19.00 -60.00   39
 30  \w      4.00  30.00   1.00    1.00    --  -42.66  19.00 -30.00   26
 31  \w      9.00  80.00   1.00    1.00    --   42.66 -99.00-180.00   71
 32  \w     40.00  69.00   1.00    4.00    --  111.00 -45.00  30.00   29
 33  \w     33.00  72.00   1.00    4.00    --  111.00 -95.00-180.00   39
 34  \w     92.00 117.00   1.00    4.00    --  111.00-132.00 -61.51   25
 35  \w     41.00  66.00   1.00    4.00    --  111.00 -61.00 -30.00   25
 36  \w     53.00  85.00   1.00    4.00    --  111.00 -61.00-150.00   32
 37  \w    111.00 144.00   1.00    4.00    --  111.00  77.00  30.00   33
 38  \w    153.00 178.00   1.00    4.00    --  111.00  77.00  30.00   25
 39  \w     84.00 141.00   1.00    4.00    --  111.00  15.00  90.00   57
 40  \w     43.00  69.00   1.00    4.00    --  111.00 -61.00 -90.00   26
 41  \w     81.00 106.00   1.00    4.00    --  111.00 -95.00-180.00   25
 42  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00 -90.00   25
 43  \w    140.00 178.00   1.00    4.00    --  111.00  30.00 -30.00   38
 44  \w     64.00  90.00   1.00    4.00    --  111.00 -61.00  30.00   26
 45  \w    127.00 168.00   1.00    4.00    --  111.00  30.00   0.00   41
 46  \w     89.00 126.00   1.00    4.00    --  111.00  30.00 -30.00   37
 47  \w     87.00 127.00   1.00    4.00    --  111.00-144.00-155.78   40
 48  \w     87.00 155.00   1.00    4.00    --  111.00  30.00 120.00   68
 49  \w     63.00  96.00   1.00    4.00    --  111.00-125.00  30.00   33
 50  \w     40.00  72.00   1.00    4.00    --  111.00 -45.00  90.00   32
 51  \w     84.00 110.00   1.00    4.00    --  111.00-117.00-131.83   26
 52  \w     41.00  66.00   1.00    4.00    --  111.00 -61.00-120.00   25
 53  \w     87.00 112.00   1.00    4.00    --  111.00-125.00 -30.00   25
 54  \w     45.00  70.00   1.00    4.00    --  111.00-132.00 -61.51   25
 55  \w     55.00  81.00   1.00    4.00    --  111.00 -61.00   0.00   26
 56  \w     86.00 112.00   1.00    4.00    --  111.00-125.00   0.00   26
 57  \w     60.00 123.00   1.00    4.00    --  111.00-138.00  72.64   63
 58  \w     -1.00  24.00   1.00    1.00    --   34.00  88.00 113.76   25
 59  \w      6.00  31.00   1.00    1.00    --   38.00  78.00   3.99   25
 60  \w      2.00  27.00   1.00    1.00    --   38.00  90.00 -78.57   25
 61  \w   -115.00 -22.00   1.00    1.00    --  -42.66 -38.00-120.00   93
 62  \w    -77.00 -26.00   1.00    1.00    --  -42.66 -38.00 -30.00   51
 63  \w    -68.00 -22.00   1.00    1.00    --  -42.66 -38.00 120.00   46
 64  \w   -114.00 -84.00   1.00    1.00    --  -42.66 -38.00 -30.00   30
 65  \w     14.00  42.00   1.00    1.00    --   46.00  82.00  23.92   28
 66  \w     13.00  38.00   1.00    1.00    --   46.00  82.00-110.09   25
 67  \w     14.00  39.00   1.00    1.00    --   46.00  79.00-141.04   25
 68  \w     14.00  39.00   1.00    1.00    --   46.00  81.00 134.58   25
 69  \w     28.00  54.00   1.00    1.00    --   58.00  71.00 -59.78   26
 70  \w     29.00  55.00   1.00    1.00    --   58.00  69.00 -18.49   26
 71  \w     32.00  58.00   1.00    1.00    --   62.00  71.00  -3.12   26
 72  \w    108.00 133.00   1.00    1.00    --   62.00  71.00  -3.12   25
 73  \w     36.00  61.00   1.00    1.00    --   66.00  70.00  73.06   25
 74  \w     36.00  62.00   1.00    1.00    --   66.00  70.00 121.04   26
 75  \w     37.00  63.00   1.00    1.00    --   66.00  69.00-121.60   26
 76  \w    111.00 137.00   1.00    1.00    --   66.00  70.00 -98.40   26
 77  \w     36.00  62.00   1.00    1.00    --   66.00  70.00 151.03   26
 78  \w     36.00  62.00   1.00    1.00    --   66.00  70.00 -98.40   26
 79  \w     40.00  65.00   1.00    1.00    --   70.00  71.00 -63.11   25
 80  \w     41.00  67.00   1.00    1.00    --   70.00  71.00 159.33   26
 81  \w     42.00  68.00   1.00    1.00    --   70.00  68.00  91.71   26
 82  \w     81.00 108.00   1.00    1.00    --   70.00  71.00-165.19   27
 83  \w     40.00  65.00   1.00    1.00    --   70.00  71.00-165.19   25
 84  \w    103.00 129.00   1.00    1.00    --   70.00  71.00  19.84   26
 85  \w     40.00  66.00   1.00    1.00    --   70.00  71.00  19.84   26
 86  \w     45.00  71.00   1.00    1.00    --   74.00  69.00  26.50   26
 87  \w     45.00  71.00   1.00    1.00    --   74.00  71.00 -33.41   26
 88  \w     95.00 122.00   1.00    1.00    --   74.00  71.00 -33.41   27
 89  \w     48.00  74.00   1.00    4.00    --   78.00  70.00-115.90   26
 90  \w     49.00  75.00   1.00    4.00    --   78.00  67.00 156.51   26
 91  \w     58.00  84.00   1.00    4.00    --   82.00  62.00 -48.30   26
 92  \w     52.00  78.00   1.00    4.00    --   82.00  71.00  23.92   26
 93  \w     57.00  84.00   1.00    4.00    --   86.00  67.00  45.49   27
 94  \w     59.00  84.00   1.00    4.00    --   86.00  60.00  87.83   25
 95  \w     57.00  83.00   1.00    4.00    --   86.00  68.00 -91.93   26
 96  \w     57.00  83.00   1.00    4.00    --   86.00  67.00-151.10   26
 97  \w     61.00  87.00   1.00    4.00    --   90.00  68.00-110.61   26
 98  \w     61.00  87.00   1.00    4.00    --   90.00  70.00 171.56   26
 99  \w     66.00  92.00   1.00    4.00    --   94.00  66.00-128.66   26
100  \w     68.00  94.00   1.00    4.00    --   98.00  70.00 151.03   26
101  \w     70.00  95.00   1.00    4.00    --   98.00  63.00 -53.24   25
102  \w     70.00  95.00   1.00    4.00    --   98.00  67.00 130.88   25
103  \w     70.00  97.00   1.00    4.00    --   98.00  64.00  99.88   27
104  \w     74.00 100.00   1.00    4.00    --  102.00  65.00  77.56   26
105  \w     73.00 106.00   1.00    4.00    --  102.00  66.00 -30.00   33
106  \w     72.00 112.00   1.00    4.00    --  102.00  70.00 176.75   40
107  \w     78.00 131.00   1.00    4.00    --  106.00  64.00 -46.09   53
108  \w     81.00 122.00   1.00    4.00    --  110.00  68.00 107.42   41
109  \w    138.00 167.00   1.00    4.00    --  111.00  61.00  60.00   29
110  \w     83.00 119.00   1.00    4.00    --  111.00  61.00  60.00   36
111  \w     86.00 112.00   1.00    4.00    --  111.00  61.00  90.00   26
112  \w    128.00 159.00   1.00    4.00    --  111.00  61.00 -60.00   31
113  \w     84.00 112.00   1.00    4.00    --  111.00  61.00 -60.00   28
114  \w     83.00 121.00   1.00    4.00    --  111.00  61.00   0.00   38
115  \w    133.00 165.00   1.00    4.00    --  111.00  61.00  90.00   32
116  \w    133.00 176.00   1.00    4.00    --  111.00  61.00-120.00   43
117  \w     84.00 114.00   1.00    4.00    --  111.00  61.00-120.00   30
118  \w    142.00 168.00   1.00    4.00    --  111.00  61.00 -90.00   26
119  \w     83.00 127.00   1.00    4.00    --  111.00  61.00 -90.00   44
120  \w    126.00 152.00   1.00    4.00    --  111.00  61.00 138.80   26
121  \w     83.00 109.00   1.00    4.00    --  111.00  61.00 138.80   26
122  \w    121.00 147.00   1.00    4.00    --  111.00  58.00-162.27   26
123  \w     85.00 111.00   1.00    4.00    --  111.00  58.00-162.27   26
124  \w     84.00 173.00   1.00    4.00    --  111.00  61.00-180.00   89
125  \w    148.00 174.00   1.00    4.00    --  111.00  64.00  28.56   26
126  \w     86.00 176.00   1.00    4.00    --  111.00  61.00 150.00   90
127  \w     83.00 108.00   1.00    4.00    --  111.00  64.00  28.56   25
128  \w    133.00 174.00   1.00    4.00    --  111.00  61.00-150.00   41
129  \w     83.00 129.00   1.00    4.00    --  111.00  61.00-150.00   46
130  \w     83.00 131.00   1.00    4.00    --  111.00  61.00 -30.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0173590000
_diffrn_orient_matrix_UB_12      -0.0469542000
_diffrn_orient_matrix_UB_13      -0.0422379000
_diffrn_orient_matrix_UB_21      -0.0343708000
_diffrn_orient_matrix_UB_22      -0.0462235000
_diffrn_orient_matrix_UB_23      0.0377311000
_diffrn_orient_matrix_UB_31      -0.1071030000
_diffrn_orient_matrix_UB_32      0.0071962000
_diffrn_orient_matrix_UB_33      -0.0332414000
_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  0.0360
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            214902
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.226
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.499
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83808
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             2960
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene/hexanes (vapour diffusion)'
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.190
_exptl_crystal_size_min          0.186
_exptl_transmission_factor_max   1.00000
_exptl_transmission_factor_min   0.83808
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.916
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     861
_refine_ls_number_reflns         15727
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      0.918
_refine_ls_R_factor_all          0.0266
_refine_ls_R_factor_gt           0.0249
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0984
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14678
_reflns_number_total             15727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound_1
_cod_original_cell_volume        7540.15(4)
_cod_database_code               1576716
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 Cu3 P6'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C200-C206
 1.52 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C101 \\sim C100 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106: within
1.7A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 1.7A
4. Others
 Fixed Sof: C100(0.75) C106(0.75) H10A(0.75) C105(0.75) H10C(0.75) C104(0.75)
 H10E(0.75) C103(0.75) H10G(0.75) C102(0.75) H102(0.75) C101(0.75) H10I(0.75)
 H10J(0.75) H10K(0.75) C206(0.25) H10D(0.25) H10F(0.25) H206(0.25) C202(0.25)
 H202(0.25) C203(0.25) H203(0.25) C204(0.25) H204(0.25) C205(0.25) H10B(0.25)
 C200(0.25) C201(0.25) H10H(0.25)
5.a Ternary CH refined with riding coordinates:
 C51(H51), C26(H26)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C15(H15), C34(H34), C38(H38), C69(H69), C50(H50), C36(H36), C57(H57),
 C65(H65), C13(H13), C71(H71), C53(H53), C67(H67), C19(H19), C37(H37), C48(H48),
  C16(H16), C40(H40), C42(H42), C28(H28), C44(H44), C17(H17), C32(H32),
 C46(H46), C56(H56), C63(H63), C61(H61), C35(H35), C55(H55), C18(H18), C66(H66),
  C68(H68), C11(H11), C41(H41), C47(H47), C54(H54), C49(H49), C10(H10), C9(H9),
 C73(H73), C75(H75), C29(H29), C3(H3), C43(H43), C62(H62), C21(H21), C7(H7),
 C30(H30), C74(H74), C12(H12), C59(H59), C25(H25), C72(H72), C31(H31), C6(H6),
 C4(H4), C60(H60), C22(H22), C24(H24), C5(H5), C23(H23), C106(H10A), C105(H10C),
  C104(H10E), C103(H10G), C102(H102), C202(H202), C203(H203), C204(H204),
 C205(H10B), C201(H10H)
5.c Fitted hexagon refined as free rotating group:
 C100(C106,C105,C104,C103,C102), C202(C203,C204,C205,C200,C201)
5.d Idealised Me refined as rotating group:
 C101(H10I,H10J,H10K), C206(H10D,H10F,H206)

Disorder Modelling Details: A molecule of toluene in the asymmetric unit 
was positionally disordered over two positions. As a result, it was split 
into two parts and refined with a fixed occupancy ratio of 0.75:0.25. The 
thermal parameters of the carbon atoms of the major component were 
restrained to be similar to one another through the use of the SIMU command. 
Additionally, the C(ipso)-CH3 bond length of the minor component was 
restrained to 1.52 A using the DFIX command. Approximately one molecule of 
toluene was removed from the asymmetric unit using the "solvent mask" feature 
of Olex2.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              54559
_shelx_fab_checksum              81017
_ins_header
;
TITL 028bec23 in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184  13.830096  23.242815  23.963768  90.0000 101.8081  90.0000
ZERR    4.00   0.000039   0.000057   0.000065   0.0000   0.0003   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H P Cu
UNIT 200.00 200.00 24.00 12.00
REM  CrysAlisPro recorded range (K): Min=149.9; max=150.1; aver:150.0
TEMP -123
TREF
HKLF 4
END
;
_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 1.241
_oxdiff_exptl_absorpt_empirical_full_min 0.846