Stabilization of reactive rare earth alkyl complexes through mechanistic studies.
Tanuhadi, Elias; Bair, Anna S.; Johnson, Mary; Fontaine, Philip; Klosin, Jerzy; Pal, Sudipta; Arnold, Polly L.; Chemical science 16 (2024) 280–287; doi:10.1039/d4sc05983b

data_1573279
_publ_section_title
;
 Stabilization of reactive rare earth alkyl complexes through mechanistic
 studies.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              280
_journal_page_last               287
_journal_paper_doi               10.1039/d4sc05983b
_journal_volume                  16
_journal_year                    2024
_chemical_formula_moiety         'C18 H49 N2 Si3 Sm'
_chemical_formula_sum            'C18 H49 N2 Si3 Sm'
_chemical_formula_weight         528.21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-10
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-07-10 deposited with the CCDC.	2024-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.87370(10)
_cell_length_b                   16.22530(10)
_cell_length_c                   17.35450(10)
_cell_measurement_reflns_used    47868
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      79.7010
_cell_measurement_theta_min      5.0800
_cell_volume                     2780.26(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.128a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.128a 64-bit (release 20-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.128a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_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 0.998
_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    -51.00  15.00   0.50    0.25    --  -47.95  77.00 120.00  132
  2  \w   -121.00 -35.00   0.50    0.25    --  -47.95 -40.00 -35.19  172
  3  \w    -54.00 -21.00   0.50    0.25    --  -47.95  57.00 -30.00   66
  4  \w    -61.00  25.00   0.50    0.25    --  -47.95  57.00  90.00  172
  5  \w    -50.00  25.00   0.50    0.25    --  -47.95  37.00-150.00  150
  6  \w    -61.00 -17.00   0.50    0.25    --  -47.95 125.00  30.00   88
  7  \w     61.00  88.00   0.50    0.25    --   47.95  45.00  54.15   54
  8  \w     35.00  93.00   0.50    0.25    --   47.95-125.00   0.00  116
  9  \w   -138.00-109.00   0.50    1.00    --  -91.75 -30.00  60.00   58
 10  \w     75.00 113.00   0.50    1.00    --  113.25 -88.00 -47.49   76
 11  \w     43.00  77.00   0.50    1.00    --  113.25 -77.00  60.00   68
 12  \w     43.00  69.00   0.50    1.00    --  113.25 -77.00-180.00   52
 13  \w    111.00 154.00   0.50    1.00    --  113.25  77.00  60.00   86
 14  \w    134.00 174.00   0.50    1.00    --  113.25  77.00 -60.00   80
 15  \w     96.00 137.00   0.50    1.00    --  113.25 -86.00  12.30   82
 16  \w     45.00  83.00   0.50    1.00    --  113.25 -88.00 -91.64   76
 17  \w    107.00 146.00   0.50    1.00    --  113.25  61.00 150.00   78
 18  \w    138.00 164.00   0.50    1.00    --  113.25  45.00-150.00   52
 19  \w     43.00  72.00   0.50    1.00    --  113.25 -77.00  30.00   58
 20  \w    110.00 175.00   0.50    1.00    --  113.25  77.00   0.00  130
 21  \w     78.00 105.00   0.50    1.00    --  113.25 -94.00 -90.00   54
 22  \w    149.00 178.00   0.50    1.00    --  113.25  61.00 150.00   58
 23  \w     54.00  81.00   0.50    1.00    --  113.25 -77.00 -90.00   54
 24  \w     46.00  79.00   0.50    1.00    --  113.25-125.00-120.00   66
 25  \w     83.00 109.00   0.50    1.00    --  113.25-125.00-120.00   52
 26  \w     42.00  67.00   0.50    1.00    --  113.25 -77.00-120.00   50
 27  \w     42.00  72.00   0.50    1.00    --  113.25 -77.00 150.00   60
 28  \w     42.00  72.00   0.50    1.00    --  113.25 -94.00  90.00   60
 29  \w     77.00 105.00   0.50    1.00    --  113.25 -94.00  90.00   56
 30  \w     48.00  82.00   0.50    1.00    --  113.25 -77.00 -30.00   68
 31  \w     44.00  89.00   0.50    1.00    --  113.25 -86.00  12.30   90
 32  \w     70.00 106.00   0.50    1.00    --  113.25 -94.00-120.00   72
 33  \w    152.00 178.00   0.50    1.00    --  113.25  30.00 -60.00   52
 34  \w    106.00 141.00   0.50    1.00    --  113.25  61.00 -60.00   70
 35  \w    103.00 131.00   0.50    1.00    --  113.25  30.00 -60.00   56
 36  \w    106.00 161.00   0.50    1.00    --  113.25  61.00 120.00  110
 37  \w     58.00 111.00   0.50    1.00    --  113.25-125.00 -90.00  106
 38  \w     42.00  67.00   0.50    1.00    --  113.25 -77.00   0.00   50
 39  \w     46.00  72.00   0.50    1.00    --  113.25 -77.00  90.00   52
 40  \w     57.00 106.00   0.50    1.00    --  113.25 -94.00  60.00   98
 41  \w    106.00 178.00   0.50    1.00    --  113.25  61.00-180.00  144
 42  \w     42.00  68.00   0.50    1.00    --  113.25 -94.00 -90.00   52
 43  \w     74.00 105.00   0.50    1.00    --  113.25 -94.00-180.00   62
 44  \w     47.00  77.00   0.50    1.00    --  113.25-125.00-150.00   60
 45  \w     86.00 111.00   0.50    1.00    --  113.25-125.00-150.00   50
 46  \w    120.00 145.00   0.50    1.00    --  113.25  77.00 120.00   50
 47  \w    151.00 177.00   0.50    1.00    --  113.25  77.00 120.00   52
 48  \w     43.00  83.00   0.50    1.00    --  113.25 -77.00 -60.00   80
 49  \w    137.00 169.00   0.50    1.00    --  113.25 125.00 -60.00   64
 50  \w     60.00  85.00   0.50    1.00    --  113.25 -94.00 -30.00   50
 51  \w     69.00 104.00   0.50    1.00    --  113.25 -94.00  30.00   70
 52  \w    132.00 178.00   0.50    1.00    --  113.25  45.00  30.00   92
 53  \w    120.00 166.00   0.50    1.00    --  113.25 125.00-150.00   92
 54  \w     66.00 104.00   0.50    1.00    --  113.25 -94.00 -60.00   76
 55  \w     70.00 103.00   0.50    1.00    --  113.25 -94.00 150.00   66
 56  \w    114.00 156.00   0.50    1.00    --  113.25  77.00  90.00   84
 57  \w    132.00 158.00   0.50    1.00    --  113.25  30.00 150.00   52
 58  \w    115.00 178.00   0.50    1.00    --  113.25  45.00  53.64  126
 59  \w    111.00 162.00   0.50    1.00    --  113.25 125.00 -30.00  102
 60  \w     72.00  98.00   0.50    1.00    --  113.25-125.00 -60.00   52
 61  \w     67.00  93.00   0.50    1.00    --  113.25-125.00 120.00   52
 62  \w    115.00 147.00   0.50    1.00    --  113.25  77.00 150.00   64
 63  \w     80.00 124.00   0.50    1.00    --  113.25  -4.00 161.71   88
 64  \w     42.00  67.00   0.50    1.00    --  113.25 -77.00 120.00   50
 65  \w     45.00 105.00   0.50    1.00    --  113.25-125.00-180.00  120
 66  \w    139.00 165.00   0.50    1.00    --  113.25 125.00 150.00   52
 67  \w    131.00 169.00   0.50    1.00    --  113.25  30.00   0.00   76
 68  \w     78.00 106.00   0.50    1.00    --  113.25 -94.00-150.00   56
 69  \w     60.00 106.00   0.50    1.00    --  113.25 -94.00 120.00   92
 70  \w    106.00 176.00   0.50    1.00    --  113.25  61.00-120.00  140
 71  \w     91.00 124.00   0.50    1.00    --  113.25 -88.00 -91.64   66
 72  \w    101.00 134.00   0.50    1.00    --  113.25  45.00 -60.00   66
 73  \w    105.00 161.00   0.50    1.00    --  113.25  45.00 -30.00  112
 74  \w    125.00 151.00   0.50    1.00    --  113.25  45.00   0.00   52
 75  \w    102.00 127.00   0.50    1.00    --  113.25  45.00 120.00   50
 76  \w    111.00 156.00   0.50    1.00    --  113.25  30.00  30.00   90
 77  \w    153.00 178.00   0.50    1.00    --  113.25 125.00 -90.00   50
 78  \w     92.00 132.00   0.50    1.00    --  113.25 -87.00 146.69   80
 79  \w     44.00 106.00   0.50    1.00    --  113.25 -97.00   5.12  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1114410000
_diffrn_orient_matrix_UB_12      0.0636871000
_diffrn_orient_matrix_UB_13      0.0176406000
_diffrn_orient_matrix_UB_21      0.1035983000
_diffrn_orient_matrix_UB_22      -0.0533307000
_diffrn_orient_matrix_UB_23      -0.0437322000
_diffrn_orient_matrix_UB_31      -0.0342040000
_diffrn_orient_matrix_UB_32      0.0459803000
_diffrn_orient_matrix_UB_33      -0.0752630000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0581
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            58576
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.931
_diffrn_reflns_theta_min         3.729
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.107
_exptl_absorpt_correction_T_max  0.482
_exptl_absorpt_correction_T_min  0.073
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.128a (Rigaku Oxford Diffraction, 2024)
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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             1100
_exptl_crystal_preparation
'crystallization from cold concentrated hexane solution.'
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.074
_refine_diff_density_max         1.319
_refine_diff_density_min         -1.137
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 2565 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.013(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         6043
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0311
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0552P)^2^+2.6302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                6008
_reflns_number_total             6043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla24134_refinalized
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_database_code               1573279
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Sm Si3 N4 C20 H50'
_chemical_oxdiff_usercomment     ELTA-SmTm
_shelx_estimated_absorpt_t_max   0.364
_shelx_estimated_absorpt_t_min   0.119
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C13(H13A,H13B), C1(H1A,H1B), C14(H14A,H14B), C2(H2A,H2B)
2.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C6(H6A,H6B,H6C), C18(H18A,H18B,H18C), C12(H12A,H12B,
 H12C), C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C17(H17A,H17B,H17C), C5(H5A,H5B,
 H5C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C7(H7A,H7B,H7C), C9(H9A,H9B,
 H9C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              34971
_shelx_hkl_checksum              39571
_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 1.648
_oxdiff_exptl_absorpt_empirical_full_min 0.618