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_1568534
_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         'C22 H50 La N3 O Si5'
_chemical_formula_sum            'C22 H50 La N3 O Si5'
_chemical_formula_weight         652.01
_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
_audit_creation_date             2022-04-26
_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                 90.8294(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.1647(3)
_cell_length_b                   15.1053(2)
_cell_length_c                   21.1116(3)
_cell_measurement_reflns_used    48047
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      31.0020
_cell_measurement_theta_min      2.3440
_cell_volume                     6748.65(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_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      100.0(2)
_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 0.820
_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    -77.00  11.00   0.50   10.00    --   -5.46 -61.00  28.00  176
  2  \w    -23.00  39.00   0.50   10.00    --    5.07 -99.00-150.00  124
  3  \w      9.00  77.00   0.50   10.00    --    5.07  61.00 166.00  136
  4  \w    -20.00   5.00   0.50   10.00    --    5.07 -19.00  30.00   50
  5  \w    -23.00  31.00   0.50   10.00    --    5.07 -99.00   0.00  108
  6  \w    -68.00 -25.00   0.50   10.00    --    5.07 -37.00 120.00   86
;
_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      -0.0146781000
_diffrn_orient_matrix_UB_12      0.0042673000
_diffrn_orient_matrix_UB_13      -0.0302525000
_diffrn_orient_matrix_UB_21      -0.0219836000
_diffrn_orient_matrix_UB_22      -0.0334461000
_diffrn_orient_matrix_UB_23      0.0080283000
_diffrn_orient_matrix_UB_31      -0.0206039000
_diffrn_orient_matrix_UB_32      0.0327000000
_diffrn_orient_matrix_UB_33      0.0122020000
_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  0.0556
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.820
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            80750
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.820
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.984
_diffrn_reflns_theta_min         2.144
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.461
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.791
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.53a (Rigaku Oxford Diffraction, 2022)
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    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.736
_refine_diff_density_min         -1.080
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     695
_refine_ls_number_reflns         17623
_refine_ls_number_restraints     210
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0562
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0303P)^2^+11.0841P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0842
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13294
_reflns_number_total             17623
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06442a2.cif
_cod_data_source_block           cx2692c
_cod_depositor_comments
'Adding full bibliography for 1568533--1568535.cif.'
_cod_original_cell_volume        6748.65(17)
_cod_database_code               1568534
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C25H66LaN3Si6O
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.795
_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. Restrained distances
 C7A-C2A \\sim C7B-C2A \\sim C7A-C6A \\sim C7B-C6B \\sim C6A-C5A \\sim C6B-C5B
\\sim C4B-C3B \\sim C4A-C3A
 \\sim C3A-C2A \\sim C3B-C2A \\sim C5B-C4B \\sim C5A-C4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C3A \\sim C3B \\sim C4A \\sim C4B \\sim C5A \\sim C5B \\sim C6A \\sim C6B \\sim
C7A \\sim C7B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C17A \\sim C18A \\sim C18B \\sim C20A \\sim C20B \\sim C21A \\sim C21B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=
 Sof(C7B)=Sof(H7B)=1-FVAR(1)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=
 Sof(C7A)=Sof(H7A)=FVAR(1)
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=1-FVAR(2)
 Sof(C20B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21B)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=FVAR(2)
 Sof(C17B)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18B)=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=1-FVAR(3)
 Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18A)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=FVAR(3)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C3A(H3A), C3B(H3B), C4A(H4A),
 C4B(H4B), C5A(H5A), C5B(H5B), C6A(H6A), C6B(H6B), C7A(H7A), C7B(H7B)
5.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10D,H10E,H10F), C11(H11D,H11E,H11F),
 C12(H12D,H12E,H12F), C13(H13D,H13E,H13F), C14(H14D,H14E,H14F), C15(H15D,H15E,
 H15F), C16(H16D,H16E,H16F), C17(H17G,H17H,H17I), C18(H18G,H18H,H18I), C19(H19D,
 H19E,H19F), C20(H20G,H20H,H20I), C21(H21G,H21H,H21I), C22(H22D,H22E,H22F),
 C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,
 H11C), C12A(H12A,H12B,H12C), C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C),
 C15A(H15A,H15B,H15C), C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C17B(H17D,
 H17E,H17F), C18A(H18A,H18B,H18C), C18B(H18D,H18E,H18F), C19A(H19A,H19B,H19C),
 C20A(H20D,H20E,H20F), C20B(H20A,H20B,H20C), C21A(H21D,H21E,H21F), C21B(H21A,
 H21B,H21C), C22A(H22A,H22B,H22C)
;
_shelx_res_checksum              70498
_shelx_hkl_checksum              63473
_olex2_date_sample_data_collection 2022-04-25
_olex2_date_sample_submission    2022-04-25
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in paratone oil'
_olex2_submission_original_sample_id cx2692c
_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 0.896