Cyclic Alkyl(amino)iminates (CAAIs) as Strong 2σ,4π-Electron Donor Ligands for the Stabilisation of Boranes and Diboranes(4): A Synthetic and Computational Study
Huynh, Silvia; Arrowsmith, Merle; Meier, Lukas; Dietz, Maximilian; Härterich, Marcel; Michel, Maximilian; Gärtner, Annalena; Braunschweig, Holger; Dalton Transactions  (2023) –; doi:10.1039/D3DT00298E

data_7712433
_publ_section_title
;
 Cyclic Alkyl(amino)iminates (CAAIs) as Strong 2\s,4\p-Electron Donor
 Ligands for the Stabilisation of Boranes and Diboranes(4): A Synthetic
 and Computational Study
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00298E
_journal_year                    2023
_chemical_formula_moiety         'C22 H37 B Br N3'
_chemical_formula_sum            'C22 H37 B Br N3'
_chemical_formula_weight         434.26
_chemical_name_systematic        (CAAI)BBrNMe2
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-26
_audit_creation_method           'CIF-fill 1.3i (K.Radacki, 2005-22)'
_audit_update_record
;
2023-01-19 deposited with the CCDC.	2023-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.9120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.0177(2)
_cell_length_b                   9.08810(10)
_cell_length_c                   14.5514(2)
_cell_measurement_reflns_used    16109
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.0350
_cell_measurement_theta_min      2.5730
_cell_volume                     2302.50(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.73a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.73a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.73a (Rigaku OD, 2020)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HPA
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HyPix 6000'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
 List of Runs (angles in degrees, time in seconds):
 --------------------------------------------------------------------------
  1  \w    -26.00  28.00   0.50    0.06    --  -47.70  19.00-120.00  108
  2  \w    -51.00 -14.00   0.50    0.24    --  -86.25  45.00-180.00   74
  3  \w    -82.00   2.00   0.50    0.06    --  -47.70 106.00 -41.00  168
  4  \w    -51.00 -14.00   0.50    0.24    --  -86.25  45.00 -30.00   74
  5  \w    -81.00 -13.00   0.50    0.24    --  -86.25 106.00 -41.00  136
  6  \w    -27.00  26.00   0.50    0.06    --   47.70 -19.00 150.00  106
  7  \w     35.00  60.00   0.50    0.24    --  107.75 -61.00  60.00   50
  8  \w     39.00  71.00   0.50    0.24    --  107.75 -61.00  90.00   64
  9  \w     36.00  68.00   0.50    0.24    --  107.75 -61.00  30.00   64
 10  \w     38.00  69.00   0.50    0.24    --  107.75 -61.00 -30.00   62
 11  \w     41.00  67.00   0.50    0.24    --  107.75 -94.00 -60.00   52
 12  \w     75.00 101.00   0.50    0.24    --  107.75 -94.00 -60.00   52
 13  \w     80.00 107.00   0.50    0.24    --  107.75-125.00   0.00   54
 14  \w     76.00 111.00   0.50    0.24    --  107.75-125.00  60.00   70
 15  \w     37.00 111.00   0.50    0.24    --  107.75-125.00 -60.00  148
 16  \w     35.00 107.00   0.50    0.24    --  107.75-106.00-140.00  144
 17  \w     37.00  85.00   0.50    0.24    --  107.75 -94.00 -30.00   96
 18  \w     35.00  99.00   0.50    0.24    --  107.75 -94.00-120.00  128
 19  \w     36.00  68.00   0.50    0.24    --  107.75 -61.00-120.00   64
 20  \w     35.00  65.00   0.50    0.24    --  107.75 -61.00-150.00   60
 21  \w     35.00  73.00   0.50    0.24    --  107.75-117.00-167.73   76
 22  \w     35.00 102.00   0.50    0.24    --  107.75-125.00-150.00  134
 23  \w     19.00  85.00   0.50    0.06    --   47.70-106.00-140.00  132
 24  \w     39.00  65.00   0.50    0.24    --  107.75-125.00   0.00   52
 25  \w     36.00  72.00   0.50    0.24    --  107.75-125.00  60.00   72
 26  \w    133.00 176.00   0.50    0.24    --  107.75  61.00-150.00   86
 27  \w    124.00 160.00   0.50    0.24    --  107.75 125.00-180.00   72
 28  \w    105.00 178.00   0.50    0.24    --  107.75 106.00 -41.00  146
 29  \w    144.00 176.00   0.50    0.24    --  107.75 125.00  30.00   64
 30  \w    121.00 150.00   0.50    0.24    --  107.75 125.00 120.00   58
 31  \w     95.00 140.00   0.50    0.24    --  107.75 125.00  30.00   90
 32  \w     99.00 178.00   0.50    0.24    --  107.75  45.00  30.00  158
 33  \w   -119.00 -73.00   0.50    0.06    --  -47.70-125.00  30.00   92
 34  \w   -119.00 -73.00   0.50    0.06    --  -47.70-125.00 -30.00   92
 35  \w   -119.00 -73.00   0.50    0.06    --  -47.70-125.00   0.00   92
 36  \w   -159.00 -83.00   0.50    0.24    --  -86.25-106.00-140.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
;
 CrysAlisPro convention (1999,Acta A55,543-557)
;
_diffrn_orient_matrix_UB_11      0.0851922000
_diffrn_orient_matrix_UB_12      -0.0030347000
_diffrn_orient_matrix_UB_13      0.0557733000
_diffrn_orient_matrix_UB_21      -0.0074038000
_diffrn_orient_matrix_UB_22      -0.1641866000
_diffrn_orient_matrix_UB_23      0.0225922000
_diffrn_orient_matrix_UB_31      0.0228245000
_diffrn_orient_matrix_UB_32      -0.0422211000
_diffrn_orient_matrix_UB_33      -0.0914933000
_diffrn_radiation_monochromator  'multi-layer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0495
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24690
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.319
_diffrn_reflns_theta_min         2.538
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet X-ray Source'
_exptl_absorpt_coefficient_mu    2.495
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.41.73a (Rigaku Oxford Diffraction, 2020) Empirical 
 absorption correction using spherical harmonics, implemented in SCALE3 
 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       plate
_exptl_crystal_F_000             920
_exptl_crystal_preparation
;
 Crystalls were grown from saturated solution. For data collection the 
 crystal was immersed in a film of perfluoropolyether oil, mounted on a 
 polyimide loop and transferred to stream of cold nitrogen (Oxford Cryostream 
 800).
;
_exptl_crystal_size_max          0.410
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.070
_refine_diff_density_max         0.650
_refine_diff_density_min         -0.766
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4836
_refine_ls_number_restraints     104
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0648P)^2^+2.1521P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4495
_reflns_number_total             4836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00298e2.cif
_cod_data_source_block           MaHa036_SiHu_a
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7712433
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.428
_shelx_estimated_absorpt_t_max   0.845
_shelx_res_checksum              49249
_shelx_hkl_checksum              15073