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_1568533
_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         'C31 H64 La N3 O Si6'
_chemical_formula_sum            'C31 H64 La N3 O Si6'
_chemical_formula_weight         802.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-08-10 deposited with the CCDC.	2023-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0920(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6736(2)
_cell_length_b                   18.4590(3)
_cell_length_c                   20.0226(3)
_cell_measurement_reflns_used    36766
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.9420
_cell_measurement_theta_min      2.3230
_cell_volume                     4308.25(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (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 1.000
_diffrn_measured_fraction_theta_max 0.873
_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     23.00  62.00   0.50    4.03    --   13.12-129.00 -37.00   78
  2  \w     48.00  79.00   0.50    4.03    --   13.12-178.00   0.00   62
  3  \w     39.00  64.00   0.50    4.03    --   13.12-178.00-180.00   50
  4  \w    -75.00   1.00   0.50    4.03    --  -13.59 -57.00-150.00  152
  5  \w    -26.00  55.00   0.50    4.03    --  -13.59  20.00-178.00  162
  6  \w    -62.00 -14.00   0.50    3.00    --   13.12 -21.00  14.00   96
  7  \w     39.00  67.00   0.50    3.00    --   13.12-178.00 -30.00   56
  8  \w    -28.00   3.00   0.50    3.00    --   13.12 -19.00 -60.00   62
  9  \w    -73.00 -43.00   0.50    3.00    --  -13.59 178.00  30.00   60
;
_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      -0.0316542000
_diffrn_orient_matrix_UB_12      -0.0013693000
_diffrn_orient_matrix_UB_13      -0.0312285000
_diffrn_orient_matrix_UB_21      0.0495931000
_diffrn_orient_matrix_UB_22      0.0106430000
_diffrn_orient_matrix_UB_23      -0.0164693000
_diffrn_orient_matrix_UB_31      0.0154781000
_diffrn_orient_matrix_UB_32      -0.0368947000
_diffrn_orient_matrix_UB_33      -0.0035845000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.873
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            61050
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.873
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.738
_diffrn_reflns_theta_min         2.037
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.184
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.605
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (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    1.237
_exptl_crystal_description       plate
_exptl_crystal_F_000             1680
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.229
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.545
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         15032
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0315
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0178P)^2^+2.9324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0583
_refine_ls_wR_factor_ref         0.0619
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12004
_reflns_number_total             15032
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06442a2.cif
_cod_data_source_block           cx2505
_cod_depositor_comments
'Adding full bibliography for 1568533--1568535.cif.'
_cod_database_code               1568533
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C31H64LaN3OSi6
_diffrn_oxdiff_digest_frames
;
01622561904a95f70a799bd72b6ffea2be003765179
;
_diffrn_oxdiff_digest_hkl
;
0152592605fa71e0444732e1fc20fa784d5a1f
;
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13)
2.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              16436
_shelx_hkl_checksum              12656
_olex2_date_sample_data_collection 2021-10-25
_olex2_date_sample_submission    2021-10-25
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with Paratone oil'
_olex2_submission_original_sample_id cx2505
_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 1.070
_oxdiff_exptl_absorpt_empirical_full_min 0.888