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_1573280
_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 P2 Sc Si3'
_chemical_formula_sum            'C18 H49 P2 Sc Si3'
_chemical_formula_weight         456.74
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-04-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-25 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                   16.9327(2)
_cell_length_b                   9.51690(10)
_cell_length_c                   18.2023(2)
_cell_measurement_reflns_used    34700
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.8290
_cell_measurement_theta_min      4.8540
_cell_volume                     2933.24(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.119a (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    'SHELXS  (Sheldrick, 2008)'
_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 0.995
_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    -70.00  16.00   0.50    0.42    --  -47.81  77.00  60.00  172
  2  \w    -85.00 -16.00   0.50    0.42    --  -47.81 125.00 120.00  138
  3  \w    -63.00  12.00   0.50    0.42    --  -47.81  57.00-150.00  150
  4  \w     -4.00  26.00   0.50    0.42    --  -47.81  19.00-180.00   60
  5  \w    -30.00   6.00   0.50    0.42    --  -47.81  57.00-150.00   72
  6  \w    -11.00  22.00   0.50    0.42    --  -47.81  19.00 -60.00   66
  7  \w    -15.00  25.00   0.50    0.42    --  -47.81  19.00 -30.00   80
  8  \w    -26.00  -1.00   0.50    0.42    --   47.81 -19.00-180.00   50
  9  \w    -23.00  60.00   0.50    0.42    --   47.81 -57.00 -90.00  166
 10  \w     66.00  92.00   0.50    0.42    --   47.81-125.00 150.00   52
 11  \w    -25.00   7.00   0.50    0.42    --   47.81 -19.00   0.00   64
 12  \w    -26.00   7.00   0.50    0.42    --   47.81 -19.00 -30.00   66
 13  \w    -26.00   8.00   0.50    0.42    --   47.81 -19.00  30.00   68
 14  \w   -132.00 -97.00   0.50    1.66    --  -91.75 -48.00  31.03   70
 15  \w     42.00  67.00   0.50    1.66    --  113.25 -61.00  30.00   50
 16  \w     66.00 107.00   0.50    1.66    --  113.25-125.00-180.00   82
 17  \w     43.00  70.00   0.50    1.66    --  113.25 -61.00  90.00   54
 18  \w     43.00  68.00   0.50    1.66    --  113.25 -94.00 150.00   50
 19  \w    102.00 141.00   0.50    1.66    --  113.25  30.00 -90.00   78
 20  \w     44.00  70.00   0.50    1.66    --  113.25 -61.00 150.00   52
 21  \w     55.00  81.00   0.50    1.66    --  113.25 -85.00 154.30   52
 22  \w    107.00 145.00   0.50    1.66    --  113.25  61.00-120.00   76
 23  \w     44.00  69.00   0.50    1.66    --  113.25 -61.00 -90.00   50
 24  \w    103.00 145.00   0.50    1.66    --  113.25  45.00-150.00   84
 25  \w    138.00 163.00   0.50    1.66    --  113.25  61.00  30.00   50
 26  \w     73.00 104.00   0.50    1.66    --  113.25 -94.00 150.00   62
 27  \w     45.00  81.00   0.50    1.66    --  113.25-125.00  60.00   72
 28  \w    142.00 178.00   0.50    1.66    --  113.25  45.00  60.00   72
 29  \w     42.00 106.00   0.50    1.66    --  113.25 -94.00-120.00  128
 30  \w     46.00 106.00   0.50    1.66    --  113.25 -94.00  90.00  120
 31  \w     57.00 104.00   0.50    1.66    --  113.25 -94.00 -90.00   94
 32  \w     46.00 106.00   0.50    1.66    --  113.25 -94.00  60.00  120
 33  \w     44.00  71.00   0.50    1.66    --  113.25 -61.00   0.00   54
 34  \w    136.00 170.00   0.50    1.66    --  113.25  61.00 -30.00   68
 35  \w    101.00 136.00   0.50    1.66    --  113.25  45.00  30.00   70
 36  \w     96.00 134.00   0.50    1.66    --  113.25 -77.00-180.00   76
 37  \w     53.00  78.00   0.50    1.66    --  113.25 -77.00-180.00   50
 38  \w    145.00 171.00   0.50    1.66    --  113.25  77.00  60.00   52
 39  \w    108.00 155.00   0.50    1.66    --  113.25  30.00 120.00   94
 40  \w    101.00 160.00   0.50    1.66    --  113.25  45.00 120.00  118
 41  \w    116.00 175.00   0.50    1.66    --  113.25 125.00 120.00  118
 42  \w    102.00 135.00   0.50    1.66    --  113.25  45.00  60.00   66
 43  \w     97.00 136.00   0.50    1.66    --  113.25 -77.00 120.00   78
 44  \w    110.00 170.00   0.50    1.66    --  113.25  77.00 -60.00  120
 45  \w     81.00 111.00   0.50    1.66    --  113.25-125.00  30.00   60
 46  \w     56.00 104.00   0.50    1.66    --  113.25 -94.00 120.00   96
 47  \w     44.00  76.00   0.50    1.66    --  113.25-125.00  30.00   64
 48  \w     43.00  78.00   0.50    1.66    --  113.25 -77.00 150.00   70
 49  \w     44.00 106.00   0.50    1.66    --  113.25 -94.00 -30.00  124
 50  \w     77.00 106.00   0.50    1.66    --  113.25 -94.00  30.00   58
 51  \w    113.00 139.00   0.50    1.66    --  113.25  77.00  60.00   52
 52  \w    129.00 170.00   0.50    1.66    --  113.25  61.00  90.00   82
 53  \w     74.00 105.00   0.50    1.66    --  113.25 -94.00-180.00   62
 54  \w    113.00 139.00   0.50    1.66    --  113.25  60.00-109.74   52
 55  \w    149.00 175.00   0.50    1.66    --  113.25  60.00-109.74   52
 56  \w     71.00 104.00   0.50    1.66    --  113.25 -94.00   0.00   66
 57  \w     44.00  71.00   0.50    1.66    --  113.25 -61.00-120.00   54
 58  \w    135.00 177.00   0.50    1.66    --  113.25  61.00-180.00   84
 59  \w     84.00 110.00   0.50    1.66    --  113.25-125.00  90.00   52
 60  \w     64.00 109.00   0.50    1.66    --  113.25-125.00 120.00   90
 61  \w     53.00  79.00   0.50    1.66    --  113.25 -77.00   0.00   52
 62  \w    110.00 135.00   0.50    1.66    --  113.25 -77.00   0.00   50
 63  \w    102.00 157.00   0.50    1.66    --  113.25  30.00-150.00  110
 64  \w    101.00 127.00   0.50    1.66    --  113.25  15.00  90.00   52
 65  \w     86.00 111.00   0.50    1.66    --  113.25-125.00   0.00   50
 66  \w     67.00  93.00   0.50    1.66    --  113.25 -94.00 -60.00   52
 67  \w     44.00  69.00   0.50    1.66    --  113.25-125.00 -90.00   50
 68  \w    102.00 133.00   0.50    1.66    --  113.25  15.00  60.00   62
 69  \w    111.00 139.00   0.50    1.66    --  113.25  30.00 -60.00   56
 70  \w    109.00 136.00   0.50    1.66    --  113.25  30.00  90.00   54
 71  \w    134.00 160.00   0.50    1.66    --  113.25 125.00  60.00   52
 72  \w     61.00 105.00   0.50    1.66    --  113.25-125.00-120.00   88
 73  \w     82.00 108.00   0.50    1.66    --  113.25-125.00 -60.00   52
 74  \w     66.00 107.00   0.50    1.66    --  113.25-125.00 -30.00   82
 75  \w    120.00 178.00   0.50    1.66    --  113.25  61.00 120.00  116
 76  \w    136.00 162.00   0.50    1.66    --  113.25  61.00 150.00   52
 77  \w    124.00 150.00   0.50    1.66    --  113.25  30.00-180.00   52
 78  \w    110.00 156.00   0.50    1.66    --  113.25  30.00 -30.00   92
 79  \w    118.00 170.00   0.50    1.66    --  113.25  15.00-180.00  104
 80  \w    128.00 154.00   0.50    1.66    --  113.25 125.00-150.00   52
 81  \w    117.00 143.00   0.50    1.66    --  113.25 125.00-120.00   52
 82  \w    136.00 161.00   0.50    1.66    --  113.25 125.00  90.00   50
 83  \w    103.00 140.00   0.50    1.66    --  113.25 -85.00 154.30   74
 84  \w     60.00  86.00   0.50    1.66    --  113.25 -77.00-150.00   52
 85  \w    111.00 136.00   0.50    1.66    --  113.25 -77.00-150.00   50
 86  \w    108.00 133.00   0.50    1.66    --  113.25 -77.00 -90.00   50
 87  \w     87.00 113.00   0.50    1.66    --  113.25 -88.00 -44.45   52
 88  \w     53.00  78.00   0.50    1.66    --  113.25 -88.00 -44.45   50
;
_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      0.0761335000
_diffrn_orient_matrix_UB_12      -0.0135845000
_diffrn_orient_matrix_UB_13      -0.0458376000
_diffrn_orient_matrix_UB_21      -0.0139335000
_diffrn_orient_matrix_UB_22      -0.1593840000
_diffrn_orient_matrix_UB_23      -0.0070576000
_diffrn_orient_matrix_UB_31      -0.0478886000
_diffrn_orient_matrix_UB_32      0.0247116000
_diffrn_orient_matrix_UB_33      -0.0707707000
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            62263
_diffrn_reflns_point_group_measured_fraction_full 0.929
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.445
_diffrn_reflns_theta_min         4.859
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.339
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.348
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.119a (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 orangish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.034
_exptl_crystal_description       prism
_exptl_crystal_F_000             1000
_exptl_crystal_preparation
'crystallization from concentrated cold hexane solution.'
_exptl_crystal_recrystallization_method
'crystallization from concentrated cold hexane solution.'
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.218
_exptl_crystal_size_min          0.129
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.360
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 2361 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         5912
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0598
_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^)+(0.0459P)^2^+4.6572P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1431
_refine_ls_wR_factor_ref         0.1435
_reflns_Friedel_coverage         0.795
_reflns_Friedel_fraction_full    0.854
_reflns_Friedel_fraction_max     0.843
_reflns_number_gt                5815
_reflns_number_total             5912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla24060_refinalized
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_database_code               1573280
_chemical_oxdiff_formula         'Sc Si3 C15 H15 P2'
_chemical_oxdiff_usercomment     'Sc dmpe'
_shelx_estimated_absorpt_t_max   0.604
_shelx_estimated_absorpt_t_min   0.402
_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. Uiso/Uaniso restraints and constraints
Uanis(Si1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
3.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C3(H3A,H3B), C2(H2A,H2B), C15(H15A,H15B)
3.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C17(H17A,H17B,H17C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C5(H5A,H5B,H5C), C12(H12B,H12A,H12C), C13(H13A,H13B,H13C), C7(H7A,H7B,H7C),
 C4(H4A,H4B,H4C), C11(H11A,H11B,H11C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C),
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              99696
_shelx_hkl_checksum              74576
_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 1.452
_oxdiff_exptl_absorpt_empirical_full_min 0.664