Catalytic Hydroboration of α,β-Unsaturated Ketones Using β-Diketiminate Magnesium Hydride and Mechanistic Insights
Das, Anubhab; Mukhopadhyay, Sayantan; Rajput, Sagrika; Nembenna, Sharanappa; Dalton Transactions  (2026) –; doi:10.1039/D6DT00286B

data_7720678
_publ_section_title
;
 Catalytic hydroboration of &#x3b1;,&#x3b2;-unsaturated ketones using
 &#x3b2;-diketiminate magnesium hydride and mechanistic insights.
;
_journal_issue                   15
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6056
_journal_page_last               6066
_journal_paper_doi               10.1039/d6dt00286b
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C70 H82.50 Mg2 N4 O2'
_chemical_formula_sum            'C70 H82.5 Mg2 N4 O2'
_chemical_formula_weight         1060.52
_chemical_name_common            'Magnesium alkoxide complex'
_chemical_name_systematic        Intermediate_Int_1
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-10-13 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                70.3430(10)
_cell_angle_beta                 68.974(2)
_cell_angle_gamma                72.7130(10)
_cell_formula_units_Z            1
_cell_length_a                   10.6672(2)
_cell_length_b                   12.4690(2)
_cell_length_c                   13.4602(2)
_cell_measurement_reflns_used    20387
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.0910
_cell_measurement_theta_min      3.6520
_cell_volume                     1541.70(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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    -65.00  28.00   0.50    0.99    --  -38.50  82.00  44.00  186
  2  \w    -17.00  75.00   0.50    0.99    --   48.81 -82.00 -77.00  184
  3  \w    103.00 168.00   0.50    3.96    --  102.00  82.00  44.00  130
  4  \w     36.00 128.00   0.50    3.96    --  102.00 -82.00 -77.00  184
  5  \w    -44.00  31.00   0.50    0.99    --  -38.50  19.00  90.00  150
  6  \w    -44.00  31.00   0.50    0.99    --  -38.50  19.00  30.00  150
  7  \w   -101.00 -27.00   0.50    0.99    --  -38.50 -57.00 -90.00  148
  8  \w    -14.00  60.00   0.50    0.99    --   48.81 -57.00 120.00  148
  9  \w     37.00 112.00   0.50    0.99    --   48.81  57.00  60.00  150
 10  \w     28.00  98.00   0.50    0.99    --   48.81-125.00 -60.00  140
 11  \w     99.00 170.00   0.50    3.96    --  102.00  30.00 120.00  142
 12  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00  90.00  144
 13  \w     98.00 167.00   0.50    3.96    --  102.00  45.00-150.00  138
 14  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00-120.00  144
 15  \w     39.00 115.00   0.50    3.96    --  102.00 -61.00  60.00  152
 16  \w    103.00 167.00   0.50    3.96    --  102.00  77.00 -90.00  128
 17  \w     99.00 170.00   0.50    3.96    --  102.00  30.00   0.00  142
 18  \w     38.00 107.00   0.50    3.96    --  102.00 -45.00 -30.00  138
 19  \w     38.00 125.00   0.50    3.96    --  102.00 -77.00  90.00  174
 20  \w     39.00 115.00   0.50    3.96    --  102.00 -61.00 -30.00  152
 21  \w     98.00 167.00   0.50    3.96    --  102.00  45.00-120.00  138
 22  \w    103.00 167.00   0.50    3.96    --  102.00  77.00  30.00  128
 23  \w     38.00 107.00   0.50    3.96    --  102.00 -45.00  90.00  138
 24  \w     39.00 112.00   0.50    3.96    --  102.00-125.00   0.00  146
 25  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00-180.00  144
 26  \w     98.00 167.00   0.50    3.96    --  102.00  45.00 -60.00  138
 27  \w     39.00 115.00   0.50    3.96    --  102.00 -61.00-120.00  152
 28  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00-150.00  144
 29  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00   0.00  144
 30  \w    103.00 167.00   0.50    3.96    --  102.00  77.00-180.00  128
 31  \w     34.00 106.00   0.50    3.96    --  102.00 -94.00 -30.00  144
 32  \w     98.00 167.00   0.50    3.96    --  102.00  45.00 -30.00  138
 33  \w     37.00 112.00   0.50    0.99    --   48.81  57.00 150.00  150
 34  \w     37.00 112.00   0.50    0.99    --   48.81  57.00-150.00  150
 35  \w     37.00 112.00   0.50    0.99    --   48.81  57.00 -30.00  150
 36  \w     37.00 112.00   0.50    0.99    --   48.81  57.00 -90.00  150
 37  \w     37.00 112.00   0.50    0.99    --   48.81  57.00   0.00  150
 38  \w     37.00 112.00   0.50    0.99    --   48.81  57.00-120.00  150
 39  \w     37.00 112.00   0.50    0.99    --   48.81  57.00  90.00  150
 40  \w     98.00 167.00   0.50    3.96    --  102.00  45.00 150.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0436
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            29965
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.256
_diffrn_reflns_theta_min         3.641
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79405
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       block
_exptl_crystal_F_000             570
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene-d6'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.437
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         6263
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0502
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0621P)^2^+0.9487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1297
_refine_ls_wR_factor_ref         0.1313
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5894
_reflns_number_total             6263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00286b2.cif
_cod_data_source_block           intermediate_int_1
_cod_depositor_comments          'Adding full bibliography for 7720678.cif.'
_cod_original_formula_sum        'C70 H82.50 Mg2 N4 O2'
_cod_database_code               7720678
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C00Z(0.75) H00P(0.75) H00Q(0.75) C012(0.75) H01G(0.75) H01H(0.75)
 H01I(0.75) C10(0.25) H10A(0.25) H10B(0.25) H10C(0.25) C11(0.25) H11A(0.25)
 H11B(0.25) C4(0.75) H4A(0.75) H4B(0.75) H4C(0.75) C12(0.25)
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B), C00O(H00E,H00G), C00T(H00H,H00I), C00Z(H00P,H00Q), C11(H11A,
 H11B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C00C(H00C), C00D(H00D), C00F(H00F), C00J(H00J), C00K(H00K),
 C00L(H00L), C00R(H00R), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X)
3.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C00Y(H00M,H00N,H00O), C010(H01A,H01B,H01C),
 C011(H01D,H01E,H01F), C012(H01G,H01H,H01I), C10(H10A,H10B,H10C), C4(H4A,H4B,
 H4C)
;
_shelx_res_checksum              3765
_shelx_hkl_checksum              80209
_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
;