Dehydrogenation of Ammonia-Borane Employing an Air-stable, Phosphine-free Molecular Nickel Pincer Catalyst
Mondal, Bijan; Mohanty, Aisa; Daw, Prosenjit; Dalton Transactions  (2026) –; doi:10.1039/D5DT02924D

data_7720000
_publ_section_title
;
 Dehydrogenation of Ammonia-Borane Employing an Air-stable, Phosphine-free
 Molecular Nickel Pincer Catalyst
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02924D
_journal_year                    2026
_chemical_formula_moiety         'C25 H29 Br2 N5 Ni'
_chemical_formula_sum            'C25 H29 Br2 N5 Ni'
_chemical_formula_weight         618.06
_chemical_name_systematic        NNNNiBr
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-20 deposited with the CCDC.	2025-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.04470(10)
_cell_length_b                   28.1677(2)
_cell_length_c                   9.31320(10)
_cell_measurement_reflns_used    62160
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      74.8620
_cell_measurement_theta_min      3.0900
_cell_volume                     2372.67(4)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_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_temperature      100.15
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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     14.00 117.00   0.50    0.05    --   43.13  77.00-180.00  206
  2  \w     14.00 117.00   0.50    0.05    --   43.13  77.00  60.00  206
  3  \w    -23.00  38.00   0.50    0.05    --  -43.13  19.00  60.00  122
  4  \w    -63.00 -29.00   0.50    0.12    -- -103.00  61.00  60.00   68
  5  \w   -100.00 -51.00   0.50    0.12    -- -103.00  77.00 -90.00   98
  6  \w     14.00 117.00   0.50    0.05    --   43.13  77.00-120.00  206
  7  \w     14.00 117.00   0.50    0.05    --   43.13  77.00 -60.00  206
  8  \w     14.00 117.00   0.50    0.05    --   43.13  77.00 -60.00  206
  9  \w     14.00 117.00   0.50    0.05    --   43.13  77.00   0.00  206
 10  \w     14.00 117.00   0.50    0.05    --   43.13  77.00  90.00  206
 11  \w     21.00 117.00   0.50    0.05    --   43.13  57.00  90.00  192
 12  \w     12.00 124.00   0.50    0.05    --   43.13  19.00  90.00  224
 13  \w     14.00 117.00   0.50    0.05    --   43.13  77.00  60.00  206
 14  \w     21.00 117.00   0.50    0.05    --   43.13  57.00-180.00  192
 15  \w     83.00 178.00   0.50    0.12    --  108.06 119.00-100.00  190
 16  \w     58.00 116.00   0.50    0.05    --   43.13 159.00  53.00  116
 17  \w     58.00 116.00   0.50    0.05    --   43.13 159.00  53.00  116
 18  \w     57.00 159.00   0.50    0.12    --  108.06 159.00  53.00  204
 19  \w     36.00 118.00   0.50    0.05    --   43.13-159.00  20.00  164
 20  \w     36.00 112.00   0.50    0.12    --  108.06-125.00 -60.00  152
 21  \w     36.00 135.00   0.50    0.12    --  108.06-159.00  20.00  198
 22  \w     36.00 135.00   0.50    0.12    --  108.06-159.00  20.00  198
 23  \w     81.00 106.00   0.50    0.12    --  108.06 -95.00  30.00   50
 24  \w     34.00  99.00   0.50    0.12    --  108.06 -95.00 -30.00  130
 25  \w     50.00 106.00   0.50    0.12    --  108.06 -95.00 -90.00  112
 26  \w     65.00 104.00   0.50    0.12    --  108.06 -95.00-180.00   78
 27  \w     39.00  69.00   0.50    0.12    --  108.06 -95.00  30.00   60
 28  \w     38.00 100.00   0.50    0.12    --  108.06-125.00 120.00  124
 29  \w     37.00 109.00   0.50    0.12    --  108.06-119.00 174.00  144
 30  \w     15.00  91.00   0.50    0.05    --   43.13-119.00 174.00  152
 31  \w     39.00  64.00   0.50    0.12    --  108.06 -95.00-180.00   50
 32  \w     35.00 108.00   0.50    0.12    --  108.06 -77.00 -30.00  146
 33  \w     38.00  74.00   0.50    0.12    --  108.06 -61.00-180.00   72
 34  \w     34.00  74.00   0.50    0.12    --  108.06 -61.00  60.00   80
 35  \w   -118.00 -30.00   0.50    0.05    --  -43.13 159.00  53.00  176
 36  \w   -112.00 -32.00   0.50    0.12    -- -103.00 125.00 120.00  160
 37  \w   -133.00 -45.00   0.50    0.12    -- -103.00 159.00  53.00  176
 38  \w    -91.00  -9.00   0.50    0.05    --  -43.13 119.00-100.00  164
 39  \w   -110.00 -31.00   0.50    0.12    -- -103.00 119.00-100.00  158
 40  \w   -120.00 -20.00   0.50    0.05    --  -43.13 -38.00-150.00  200
 41  \w   -100.00 -74.00   0.50    0.12    -- -103.00 -77.00-144.76   52
 42  \w   -117.00 -20.00   0.50    0.05    --  -43.13 -57.00 -60.00  194
 43  \w   -117.00 -20.00   0.50    0.05    --  -43.13 -57.00  30.00  194
 44  \w   -174.00 -74.00   0.50    0.12    -- -103.00 -77.00 150.00  200
 45  \w   -142.00 -74.00   0.50    0.12    -- -103.00 -77.00 165.75  136
 46  \w    -99.00 -74.00   0.50    0.12    -- -103.00 -77.00  60.00   50
 47  \w    -99.00 -74.00   0.50    0.12    -- -103.00 -77.00  30.00   50
 48  \w   -174.00 -74.00   0.50    0.12    -- -103.00 -77.00  30.00  200
 49  \w   -174.00-148.00   0.50    0.12    -- -103.00 -77.00  60.00   52
 50  \w   -100.00 -74.00   0.50    0.12    -- -103.00 -77.00 -30.00   52
 51  \w   -101.00 -74.00   0.50    0.12    -- -103.00 -77.00 -73.69   54
 52  \w   -110.00 -74.00   0.50    0.12    -- -103.00 -77.00-120.00   72
 53  \w   -124.00 -74.00   0.50    0.12    -- -103.00 -77.00 -90.00  100
 54  \w   -135.00-107.00   0.50    0.12    -- -103.00 -77.00-144.76   56
 55  \w   -167.00-139.00   0.50    0.12    -- -103.00 -77.00 -90.00   56
 56  \w   -172.00-127.00   0.50    0.12    -- -103.00 -77.00 -73.69   90
 57  \w   -154.00 -74.00   0.50    0.12    -- -103.00 -76.00-155.19  160
 58  \w   -119.00 -74.00   0.50    0.12    -- -103.00 -77.00 -60.00   90
 59  \w   -168.00 -74.00   0.50    0.12    -- -103.00 -76.00-165.87  188
 60  \w   -166.00 -74.00   0.50    0.12    -- -103.00 -77.00  90.00  184
 61  \w   -174.00 -74.00   0.50    0.12    -- -103.00 -76.00 179.37  200
 62  \w   -108.00 -74.00   0.50    0.12    -- -103.00 -76.00 109.00   68
 63  \w   -174.00 -74.00   0.50    0.12    -- -103.00 -76.00  95.28  200
 64  \w   -163.00-137.00   0.50    0.12    -- -103.00 -73.00   4.86   52
 65  \w   -130.00 -76.00   0.50    0.12    -- -103.00 -73.00   4.86  108
 66  \w   -102.00 -76.00   0.50    0.12    -- -103.00 -73.00 -20.60   52
 67  \w   -100.00 -74.00   0.50    0.12    -- -103.00 -76.00 -51.43   52
 68  \w   -107.00 -74.00   0.50    0.12    -- -103.00 -76.00-135.04   66
 69  \w   -102.00 -76.00   0.50    0.12    -- -103.00 -72.00 -88.58   52
 70  \w   -162.00-137.00   0.50    0.12    -- -103.00 -76.00-135.04   50
 71  \w   -173.00-147.00   0.50    0.12    -- -103.00 -72.00  -8.35   52
 72  \w   -143.00 -76.00   0.50    0.12    -- -103.00 -72.00  -8.35  134
 73  \w   -131.00 -76.00   0.50    0.12    -- -103.00 -72.00  35.90  110
 74  \w   -167.00 -76.00   0.50    0.12    -- -103.00 -72.00  56.44  182
 75  \w   -101.00 -76.00   0.50    0.12    -- -103.00 -73.00 117.18   50
 76  \w   -174.00 -76.00   0.50    0.12    -- -103.00 -71.00 125.90  196
 77  \w   -145.00-119.00   0.50    0.12    -- -103.00 -71.00 125.90   52
 78  \w   -102.00 -77.00   0.50    0.12    -- -103.00 -70.00 -30.17   50
 79  \w   -104.00 -79.00   0.50    0.12    -- -103.00 -65.00  33.81   50
 80  \w   -155.00 -79.00   0.50    0.12    -- -103.00 -65.00  62.94  152
 81  \w   -106.00 -80.00   0.50    0.12    -- -103.00 -61.00 120.00   52
 82  \w   -134.00 -78.00   0.50    0.12    -- -103.00 -67.00   5.43  112
 83  \w   -173.00 -79.00   0.50    0.12    -- -103.00 -61.00 -30.00  188
 84  \w   -174.00 -79.00   0.50    0.12    -- -103.00 -64.00 -57.92  190
 85  \w   -174.00 -77.00   0.50    0.12    -- -103.00 -70.00-113.85  194
 86  \w   -174.00 -77.00   0.50    0.12    -- -103.00 -70.00-102.05  194
 87  \w   -139.00 -80.00   0.50    0.12    -- -103.00 -48.00  88.39  118
 88  \w   -174.00 -77.00   0.50    0.12    -- -103.00-119.00 174.00  194
 89  \w   -158.00 -50.00   0.50    0.12    -- -103.00-159.00  20.00  216
 90  \w   -117.00 -50.00   0.50    0.05    --  -43.13-159.00  20.00  134
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            82923
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.352
_diffrn_reflns_theta_min         3.138
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    5.309
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73963
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.730
_exptl_crystal_description       plate
_exptl_crystal_F_000             1248
_exptl_crystal_preparation       'refluxing condtion with NiCl2(PPh3)2'
_exptl_crystal_recrystallization_method 'vapour diffusion method'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.657
_refine_diff_density_min         -0.546
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         4804
_refine_ls_number_restraints     382
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0250
_refine_ls_R_factor_gt           0.0243
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0373P)^2^+2.3097P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0658
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4640
_reflns_number_total             4804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02924d2.cif
_cod_data_source_block           pd-bm-nibr-pip_auto
_cod_database_code               7720000
_shelx_shelxl_version_number     2019/3
_diffrn_oxdiff_ac3_digest_hkl    418c8f57d01d66cc64e0a22229b604e4301141
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N5-C12 \\sim N6-C12
 with sigma of 0.02
 N5-C21 \\sim N6-C30
 with sigma of 0.02
 N5-C23 \\sim N6-C26
 with sigma of 0.02
 C21-C25 \\sim C30-C29
 with sigma of 0.02
 C22-C24 \\sim C28-C27
 with sigma of 0.02
 C22-C25 \\sim C28-C29
 with sigma of 0.02
 C23-C24 \\sim C26-C27
 with sigma of 0.02
 N5-C24 \\sim N6-C27
 with sigma of 0.04
 N5-C25 \\sim N6-C29
 with sigma of 0.04
 C12-C21 \\sim C12-C30
 with sigma of 0.04
 C12-C23 \\sim C12-C26
 with sigma of 0.04
 C21-C22 \\sim C30-C28
 with sigma of 0.04
 C21-C23 \\sim C30-C26
 with sigma of 0.04
 C22-C23 \\sim C28-C26
 with sigma of 0.04
 C24-C25 \\sim C27-C29
 with sigma of 0.04
 Br2-Ni1 \\sim Br3-Ni1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 Br3, Br2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N6)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=1-FVAR(1)
 Sof(N5)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=
 Sof(H23A)=Sof(C24)=Sof(H24A)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(1)
 Sof(Br3)=1-FVAR(2)
 Sof(Br2)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,
 H20B), C21(H21A,H21B), C22(H22A,H22B), C25(H25A,H25B), C28(H28A,H28B),
 C29(H29A,H29B), C30(H30A,H30B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C13(H13), C14(H14), C15(H15),
 C16(H16), C23(H23A), C24(H24A), C26(H26), C27(H27)
;
_olex2_exptl_crystal_mounting_method 'metigen loop'
_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
;