Backbone Deprotonation Defines a Hidden Decomposition Pathway of Diphosphine Ligands
Taylor, Logan; Dilinaer, A. Dina; Boyle, Paul D.; Drover, Marcus W.; Chemical Communications  (2026) –; doi:10.1039/D6CC01011C

data_7135623
_publ_section_title
;
 Backbone deprotonation defines a hidden decomposition pathway of
 diphosphine ligands.
;
_journal_issue                   29
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7524
_journal_page_last               7528
_journal_paper_doi               10.1039/d6cc01011c
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C20 H39 Cl Fe P2'
_chemical_formula_sum            'C20 H39 Cl Fe P2'
_chemical_formula_weight         432.75
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-11-21
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-02-02 deposited with the CCDC.	2026-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0539(2)
_cell_length_b                   12.3788(2)
_cell_length_c                   22.5477(3)
_cell_measurement_reflns_used    16398
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.2480
_cell_measurement_theta_min      4.0610
_cell_volume                     2247.95(7)
_computing_cell_refinement       'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.118a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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     99.00 127.00   0.50    0.35    --   98.16  51.00-177.00   56
  2  \w     61.00  86.00   0.50    0.35    --   51.09  51.00-177.00   50
  3  \w    113.00 156.00   0.50    0.35    --   98.16  77.00   0.00   86
  4  \w     90.00 168.00   0.50    0.35    --   98.16  57.00  90.00  156
  5  \w    143.00 171.00   0.50    0.35    --   98.16  38.00 120.00   56
  6  \w    106.00 132.00   0.50    0.35    --   98.16  38.00 120.00   52
  7  \w     82.00 129.00   0.50    0.35    --  104.00  11.00  32.04   94
  8  \w    137.00 165.00   0.50    0.35    --  104.00  11.00  32.04   56
  9  \w     71.00 118.00   0.50    0.35    --  104.00  11.00   0.81   94
 10  \w     78.00 148.00   0.50    0.35    --  104.00  11.00 -64.65  140
 11  \w    141.00 167.00   0.50    0.35    --  104.00  11.00-117.76   52
 12  \w     70.00 125.00   0.50    0.35    --  104.00  10.00-171.01  110
 13  \w     70.00  99.00   0.50    0.35    --  104.00  11.00-117.76   58
 14  \w     73.00 102.00   0.50    0.35    --  104.00  11.00 -94.55   58
 15  \w     70.00 162.00   0.50    0.35    --  104.00  10.00 106.99  184
 16  \w    103.00 152.00   0.50    0.35    --  104.00  10.00 138.43   98
 17  \w     39.00  72.00   0.50    0.35    --  104.00 -81.00 118.18   66
 18  \w     82.00 109.00   0.50    0.35    --   98.16-125.00  60.00   54
 19  \w     81.00 107.00   0.50    0.35    --   98.16-125.00  30.00   52
 20  \w     31.00  68.00   0.50    0.35    --   98.16-125.00  60.00   74
 21  \w     76.00 101.00   0.50    0.35    --   51.09-125.00-180.00   50
 22  \w     23.00  50.00   0.50    0.35    --   51.09-125.00-180.00   54
 23  \w     30.00  55.00   0.50    0.35    --   98.16-125.00-180.00   50
 24  \w     75.00 101.00   0.50    0.35    --   98.16 -99.00-150.00   52
 25  \w     81.00 107.00   0.50    0.35    --   98.16-125.00-180.00   52
 26  \w     33.00  58.00   0.50    0.35    --   98.16 -99.00-120.00   50
 27  \w     67.00 100.00   0.50    0.35    --   98.16 -99.00 -90.00   66
 28  \w     73.00 102.00   0.50    0.35    --   98.16 -99.00-180.00   58
 29  \w     83.00 109.00   0.50    0.35    --   98.16-125.00 -60.00   52
 30  \w     73.00  99.00   0.50    0.35    --   98.16 -99.00 -60.00   52
 31  \w     44.00  69.00   0.50    0.35    --  104.00 -86.00 -33.75   50
 32  \w     71.00 103.00   0.50    0.35    --  104.00 -86.00 -33.75   64
 33  \w     74.00 100.00   0.50    0.35    --   98.16 -99.00  90.00   52
 34  \w     64.00 108.00   0.50    0.35    --   98.16-125.00 120.00   88
 35  \w     73.00 102.00   0.50    0.35    --   98.16 -99.00 120.00   58
 36  \w     53.00 107.00   0.50    0.35    --  104.00 -85.00  64.23  108
 37  \w     75.00 102.00   0.50    0.35    --  104.00 -85.00  32.32   54
 38  \w     40.00  72.00   0.50    0.35    --  104.00 -85.00  32.32   64
 39  \w     39.00  68.00   0.50    0.35    --  104.00 -85.00  16.56   58
 40  \w     82.00 108.00   0.50    0.35    --  104.00 -85.00  16.56   52
 41  \w     39.00  69.00   0.50    0.35    --  104.00 -84.00  -8.37   60
 42  \w     39.00  66.00   0.50    0.35    --  104.00 -83.00 -25.29   54
 43  \w     40.00  75.00   0.50    0.35    --  104.00 -84.00 -91.79   70
 44  \w     40.00  74.00   0.50    0.35    --  104.00 -85.00-126.93   68
 45  \w     39.00  69.00   0.50    0.35    --  104.00 -83.00-163.54   60
 46  \w     39.00  69.00   0.50    0.35    --  104.00 -83.00-138.27   60
 47  \w     80.00 106.00   0.50    0.35    --  104.00 -85.00-126.93   52
 48  \w     41.00  69.00   0.50    0.35    --  104.00 -82.00  -1.59   56
 49  \w     83.00 122.00   0.50    0.35    --  104.00 -83.00 139.07   78
 50  \w    103.00 129.00   0.50    0.35    --  104.00 -83.00 174.02   52
 51  \w     39.00  74.00   0.50    0.35    --  104.00 -83.00 174.02   70
 52  \w     39.00  77.00   0.50    0.35    --  104.00 -83.00 139.07   76
 53  \w     40.00  80.00   0.50    0.35    --  104.00 -82.00  69.20   80
 54  \w    106.00 131.00   0.50    0.35    --  104.00 -82.00  69.20   50
 55  \w     99.00 130.00   0.50    0.35    --  104.00 -82.00 -46.32   62
 56  \w     42.00  70.00   0.50    0.35    --  104.00 -82.00 -46.32   56
 57  \w    -21.00  39.00   0.50    0.35    --   51.09 -51.00  36.00  120
 58  \w     39.00  65.00   0.50    0.35    --  104.00 -80.00  70.18   52
 59  \w     41.00  71.00   0.50    0.35    --  104.00 -80.00 152.25   60
 60  \w     66.00  91.00   0.50    0.35    --  104.00 -79.00 107.02   50
 61  \w     38.00  64.00   0.50    0.35    --  104.00 -79.00 107.02   52
 62  \w     39.00  64.00   0.50    0.35    --  104.00 -80.00 -18.08   50
 63  \w     38.00  66.00   0.50    0.35    --  104.00 -79.00-107.58   56
 64  \w     39.00  79.00   0.50    0.35    --  104.00 -79.00-162.54   80
 65  \w     39.00  77.00   0.50    0.35    --  104.00 -79.00 -74.68   76
 66  \w     38.00  89.00   0.50    0.35    --  104.00 -79.00 -88.08  102
 67  \w     46.00  85.00   0.50    0.35    --  104.00 -79.00-126.77   78
 68  \w     39.00  65.00   0.50    0.35    --  104.00 -78.00-172.48   52
 69  \w     93.00 126.00   0.50    0.35    --  104.00 -79.00-107.58   66
 70  \w     45.00  70.00   0.50    0.35    --  104.00 -77.00  40.41   50
 71  \w     42.00  75.00   0.50    0.35    --  104.00 -79.00  80.40   66
 72  \w     25.00  57.00   0.50    0.35    --   98.16 -51.00  36.00   64
 73  \w     38.00  64.00   0.50    0.35    --  104.00 -78.00 -66.88   52
 74  \w    -37.00  -5.00   0.50    0.35    --    2.00 115.00 -40.40   64
 75  \w   -118.00 -45.00   0.50    0.35    --  -49.97 -51.00  36.00  146
 76  \w   -147.00-106.00   0.50    0.35    --  -74.90 -51.00  36.00   82
 77  \w    -42.00  -6.00   0.50    0.35    --  -74.90  38.00   0.00   72
 78  \w    -37.00  -1.00   0.50    0.35    --  -74.90  38.00 -60.00   72
 79  \w    -41.00  -2.00   0.50    0.35    --  -74.90  38.00 -90.00   78
 80  \w    -55.00  23.00   0.50    0.35    --  -49.97  51.00-177.00  156
 81  \w    -53.00  -8.00   0.50    0.35    --  -49.97  51.00-177.00   90
 82  \w    -33.00  -3.00   0.50    0.35    --  -74.90  51.00-177.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1858197000
_diffrn_orient_matrix_UB_12      -0.0121552000
_diffrn_orient_matrix_UB_13      0.0146950000
_diffrn_orient_matrix_UB_21      -0.0089193000
_diffrn_orient_matrix_UB_22      -0.1011266000
_diffrn_orient_matrix_UB_23      -0.0397061000
_diffrn_orient_matrix_UB_31      0.0442999000
_diffrn_orient_matrix_UB_32      -0.0715040000
_diffrn_orient_matrix_UB_33      0.0536501000
_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  0.0436
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            45347
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.198
_diffrn_reflns_theta_min         3.921
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.798
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.607
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.118a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.467
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 1814 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0049(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         4719
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0301P)^2^+1.4907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0681
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                4592
_reflns_number_total             4719
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc01011c3.cif
_cod_data_source_block           Complex_1
_cod_depositor_comments
'Adding full bibliography for 7135623--7135624.cif.'
_cod_database_code               7135623
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C20 H38 Cl Fe P2'
_chemical_oxdiff_usercomment     '1310815 	LT-02-38'
_cell_oxdiff_angle_alpha         90.0035(12)
_cell_oxdiff_angle_beta          90.0010(13)
_cell_oxdiff_angle_gamma         89.9832(16)
_cell_oxdiff_length_a            8.05584(18)
_cell_oxdiff_length_b            12.3792(2)
_cell_oxdiff_length_c            22.5414(2)
_cell_oxdiff_measurement_reflns_used 16398
_cell_oxdiff_volume              2247.94(7)
_shelx_estimated_absorpt_t_max   0.746
_shelx_estimated_absorpt_t_min   0.351
_diffrn_oxdiff_digest_hkl
;
4343e2db469ce8f21bf3927f4d721b2656c3d8
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name sc26017.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-C19 \\sim C18-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C18-C20 \\sim C18-C20A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
4. Others
 Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C18(H18C,H18D),
  C19(H19A,H19B), C19A(H19C,H19D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C17(H17A,H17B,H17C),
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              47053
_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 1.789
_oxdiff_exptl_absorpt_empirical_full_min 0.752