Mechanistic study of homoleptic trisamidolanthanide-catalyzed aldehyde and ketone hydroboration. Chemically non-innocent ligand participation.
Rothbaum, Jacob O.; Motta, Alessandro; Kratish, Yosi; Marks, Tobin J.; Chemical science 14 (2023) 3247–3256; doi:10.1039/d2sc06442a

data_1568535
_publ_section_title
;
 Mechanistic study of homoleptic trisamidolanthanide-catalyzed aldehyde
 and ketone hydroboration. Chemically non-innocent ligand participation.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              3247
_journal_page_last               3256
_journal_paper_doi               10.1039/d2sc06442a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C48 H132 B6 La2 N4 O8 Si8, C7 H8'
_chemical_formula_sum            'C55 H140 B6 La2 N4 O8 Si8'
_chemical_formula_weight         1553.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-10 deposited with the CCDC.	2023-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 123.939(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.6404(7)
_cell_length_b                   15.2264(3)
_cell_length_c                   24.7520(7)
_cell_measurement_reflns_used    51282
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.2810
_cell_measurement_theta_min      2.1060
_cell_volume                     8642.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -58.00  34.00   0.50   26.00    --   13.12 -73.00 -63.00  184
  2  \w     -1.00  74.00   0.50   26.00    --   13.12  73.00  65.00  150
  3  \w    -79.00 -22.00   0.50   26.00    --  -13.59 -73.00 -63.00  114
  4  \w    -34.00  54.00   0.50   26.00    --  -13.59  73.00  65.00  176
  5  \w    -16.00  47.00   0.50   26.00    --   13.12 -99.00-150.00  126
  6  \w     16.00  47.00   0.50   26.00    --   13.12 -99.00 120.00   62
  7  \w      2.00  47.00   0.50   26.00    --   13.12 -99.00 -90.00   90
  8  \w     -3.00  37.00   0.50   26.00    --   13.12  77.00 -90.00   80
  9  \w     54.00  80.00   0.50   26.00    --   13.12  77.00 -90.00   52
 10  \w      4.00  73.00   0.50   26.00    --   13.12  57.00-150.00  138
 11  \w     -7.00  80.00   0.50   26.00    --   13.12  77.00  90.00  174
 12  \w    -20.00  47.00   0.50   26.00    --   13.12 -99.00-180.00  134
 13  \w     37.00  64.00   0.50   26.00    --   13.12-131.00 -25.74   54
 14  \w    -16.00  47.00   0.50   26.00    --   13.12 -99.00  60.00  126
 15  \w    -23.00  12.00   0.50   26.00    --   13.12 -99.00 120.00   70
 16  \w    -86.00  -6.00   0.50   26.00    --  -13.59 -37.00 150.00  160
 17  \w    -53.00  -5.00   0.50   26.00    --  -13.59 110.00 -85.21   96
 18  \w    -66.00 -22.00   0.50   26.00    --  -13.59 -77.00   0.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0246585966
_diffrn_orient_matrix_UB_12      -0.0120611896
_diffrn_orient_matrix_UB_13      0.0002661671
_diffrn_orient_matrix_UB_21      -0.0005187295
_diffrn_orient_matrix_UB_22      -0.0416137360
_diffrn_orient_matrix_UB_23      -0.0131987008
_diffrn_orient_matrix_UB_31      0.0186779339
_diffrn_orient_matrix_UB_32      -0.0170926663
_diffrn_orient_matrix_UB_33      0.0319105066
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0684
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            139797
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.337
_diffrn_reflns_theta_min         2.132
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.128
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.877
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (Rigaku Oxford Diffraction, 2021)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       plate
_exptl_crystal_F_000             3272
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.758
_refine_diff_density_min         -0.766
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 7712 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.507(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     810
_refine_ls_number_reflns         21472
_refine_ls_number_restraints     835
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0673
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0916P)^2^+2.8029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1334
_refine_ls_wR_factor_ref         0.1415
_reflns_Friedel_coverage         0.998
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                18147
_reflns_number_total             21472
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06442a2.cif
_cod_data_source_block           cx2506a
_cod_depositor_comments
'Adding full bibliography for 1568533--1568535.cif.'
_cod_database_code               1568535
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C62H46B2La2NO7Si8
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5180(16)
 0.4820(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All B(H,H,H) groups, All C(H,H,H) groups
3. Restrained distances
 C9-C7 = C7-C10 = C8-C11 = C8-C12 = C5-C2 = C6-C2 = C3-C1 = C4-C1
 1.54 with sigma of 0.02
 B3-H3D = B3-H3E = B3-H3F
 1 with sigma of 0.01
 B5-H5F = B5-H5E = B5-H5D
 1 with sigma of 0.01
 B4-H4D
 1 with sigma of 0.01
 B4-H4E
 1 with sigma of 0.01
 B6-H6E = B6-H6F = B6-H6D
 1 with sigma of 0.01
 B4-H4F
 1 with sigma of 0.01
 La2-H6F \\sim La2-H6D \\sim La2-H6E \\sim La2-H5D \\sim La2-H5F \\sim La2-H5E
\\sim La1-H3F \\sim La1-H3E
 \\sim La1-H3D
 with sigma of 0.01
 B5-H5D \\sim B5-H5E \\sim B5-H5F
 with sigma of 0.01
 H5D-H5F \\sim H5F-H5E \\sim H5E-H5D
 with sigma of 0.02
 H6D-H6E \\sim H6D-H6F \\sim H6E-H6F
 with sigma of 0.02
 H3D-H3E \\sim H3D-H3F \\sim H3E-H3F
 with sigma of 0.02
 B4-H4D \\sim B4-H4E \\sim B4-H4F
 with sigma of 0.02
 C53-C52 \\sim C52-C51 \\sim C51-C50 \\sim C50-C49 \\sim C54-C49 \\sim C54-C53
 with sigma of 0.01
 La1-H4F \\sim La1-H4E \\sim La1-H4D \\sim La1-H3D \\sim La1-H3E \\sim La1-H3F
 with sigma of 0.01
 C6-C3 \\sim C4-C5 \\sim C16-C18 \\sim C17-C15
 with sigma of 0.01
 H4D-H4F \\sim H4E-H4F \\sim H4D-H4E
 with sigma of 0.04
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C16(H16A,H16B,H16C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C35(H35A,H35B,H35C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C)
5.b Aromatic/amide H refined with riding coordinates:
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54)
5.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C),
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C34(H34A,
 H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C55(H55A,
 H55B,H55C), C24(H24A,H24B,H24C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              70577
_shelx_hkl_checksum              33921
_olex2_date_sample_data_collection 2021-10-25
_olex2_date_sample_submission    2021-10-25
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in paratone oil'
_olex2_submission_original_sample_id cx2506a
_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 1.173
_oxdiff_exptl_absorpt_empirical_full_min 0.865