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_1573276
_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 Sc Si3'
_chemical_formula_sum            'C18 H49 N2 Sc Si3'
_chemical_formula_weight         422.82
_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   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                   10.26960(10)
_cell_length_b                   15.03040(10)
_cell_length_c                   17.60830(10)
_cell_measurement_reflns_used    50206
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      79.5380
_cell_measurement_theta_min      3.7790
_cell_volume                     2717.95(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.119a 64-bit (release 08-04-2024))'
_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(11)
_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 0.994
_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     -6.00  20.00   0.50    0.12    --  -48.06  19.00 150.00   52
  2  \w    -16.00   9.00   0.50    0.12    --  -48.06  19.00 -60.00   50
  3  \w    -16.00  11.00   0.50    0.12    --  -48.06  19.00 -90.00   54
  4  \w    -62.00  24.00   0.50    0.12    --  -48.06  57.00-180.00  172
  5  \w    114.00 162.00   0.50    0.49    --  113.25 125.00-180.00   96
  6  \w    111.00 156.00   0.50    0.49    --  113.25 125.00 -30.00   90
  7  \w    116.00 142.00   0.50    0.49    --  113.25 125.00   0.00   52
  8  \w    143.00 170.00   0.50    0.49    --  113.25 125.00   0.00   54
  9  \w    139.00 165.00   0.50    0.49    --  113.25 125.00 150.00   52
 10  \w     96.00 122.00   0.50    0.49    --  113.25 125.00 150.00   52
 11  \w    113.00 139.00   0.50    0.49    --  113.25   7.00  17.77   52
 12  \w    111.00 177.00   0.50    0.49    --  113.25  77.00 -90.00  132
 13  \w    152.00 178.00   0.50    0.49    --  113.25  77.00 -60.00   52
 14  \w    114.00 140.00   0.50    0.49    --  113.25  77.00 -60.00   52
 15  \w    131.00 178.00   0.50    0.49    --  113.25  77.00 -30.00   94
 16  \w    117.00 142.00   0.50    0.49    --  113.25  77.00-180.00   50
 17  \w    144.00 178.00   0.50    0.49    --  113.25  77.00-180.00   68
 18  \w    116.00 145.00   0.50    0.49    --  113.25  77.00-120.00   58
 19  \w    117.00 142.00   0.50    0.49    --  113.25  77.00-150.00   50
 20  \w    117.00 158.00   0.50    0.49    --  113.25  77.00   0.00   82
 21  \w    123.00 171.00   0.50    0.49    --  113.25  77.00  60.00   96
 22  \w    115.00 140.00   0.50    0.49    --  113.25  61.00  90.00   50
 23  \w    121.00 146.00   0.50    0.49    --  113.25  77.00 120.00   50
 24  \w    143.00 178.00   0.50    0.49    --  113.25  77.00 150.00   70
 25  \w    147.00 173.00   0.50    0.49    --  113.25  61.00  90.00   52
 26  \w    129.00 155.00   0.50    0.49    --  113.25  61.00 150.00   52
 27  \w    106.00 141.00   0.50    0.49    --  113.25  61.00  60.00   70
 28  \w    104.00 150.00   0.50    0.49    --  113.25  45.00  60.00   92
 29  \w    113.00 139.00   0.50    0.49    --  113.25  61.00   0.00   52
 30  \w    106.00 167.00   0.50    0.49    --  113.25  30.00  90.00  122
 31  \w    102.00 152.00   0.50    0.49    --  113.25  45.00   0.00  100
 32  \w    136.00 166.00   0.50    0.49    --  113.25  45.00 -30.00   60
 33  \w    106.00 154.00   0.50    0.49    --  113.25  61.00 -60.00   96
 34  \w    101.00 147.00   0.50    0.49    --  113.25  30.00 -90.00   92
 35  \w    147.00 172.00   0.50    0.49    --  113.25  30.00-150.00   50
 36  \w    141.00 167.00   0.50    0.49    --  113.25  15.00-180.00   52
 37  \w    144.00 169.00   0.50    0.49    --  113.25  30.00-180.00   50
 38  \w    130.00 156.00   0.50    0.49    --  113.25  15.00-150.00   52
 39  \w    108.00 138.00   0.50    0.49    --  113.25  30.00-180.00   60
 40  \w    136.00 162.00   0.50    0.49    --  113.25  15.00-120.00   52
 41  \w     72.00 104.00   0.50    0.49    --  113.25   7.00  17.77   64
 42  \w    143.00 172.00   0.50    0.49    --  113.25  15.00 150.00   58
 43  \w    110.00 139.00   0.50    0.49    --  113.25  15.00 150.00   58
 44  \w     42.00  73.00   0.50    0.49    --  113.25 -77.00 120.00   62
 45  \w     43.00  69.00   0.50    0.49    --  113.25 -77.00  90.00   52
 46  \w     89.00 121.00   0.50    0.49    --  113.25 -77.00 120.00   64
 47  \w    110.00 135.00   0.50    0.49    --  113.25 -77.00   0.00   50
 48  \w     61.00  87.00   0.50    0.49    --  113.25 -77.00   0.00   52
 49  \w     73.00  99.00   0.50    0.49    --  113.25 -77.00 -60.00   52
 50  \w     49.00  75.00   0.50    0.49    --  113.25 -77.00-150.00   52
 51  \w     47.00  73.00   0.50    0.49    --  113.25 -64.00 -78.56   52
 52  \w    110.00 136.00   0.50    0.49    --  113.25 -77.00 -90.00   52
 53  \w     43.00  69.00   0.50    0.49    --  113.25 -61.00-120.00   52
 54  \w     45.00  70.00   0.50    0.49    --  113.25 -61.00   0.00   50
 55  \w     45.00  71.00   0.50    0.49    --  113.25 -61.00  60.00   52
 56  \w     42.00  70.00   0.50    0.49    --  113.25 -75.00 177.53   56
 57  \w     85.00 134.00   0.50    0.49    --  113.25 -75.00 177.53   98
 58  \w     42.00  68.00   0.50    0.49    --  113.25 -61.00 -30.00   52
 59  \w     42.00  67.00   0.50    0.49    --  113.25 -61.00 -60.00   50
 60  \w     44.00  71.00   0.50    0.49    --  113.25 -61.00 -90.00   54
 61  \w     42.00  67.00   0.50    0.49    --  113.25 -61.00-150.00   50
 62  \w     42.00  71.00   0.50    0.49    --  113.25 -61.00-180.00   58
 63  \w    -26.00   8.00   0.50    0.12    --   48.06 -19.00 -60.00   68
 64  \w    -25.00   5.00   0.50    0.12    --   48.06 -19.00 -30.00   60
 65  \w     42.00  67.00   0.50    0.49    --  113.25 -61.00 150.00   50
 66  \w     51.00  94.00   0.50    0.12    --   48.06-125.00 -90.00   86
 67  \w     44.00  70.00   0.50    0.49    --  113.25 -94.00 -90.00   52
 68  \w     45.00  71.00   0.50    0.49    --  113.25-125.00  60.00   52
 69  \w     76.00 111.00   0.50    0.49    --  113.25-125.00  90.00   70
 70  \w     80.00 111.00   0.50    0.49    --  113.25-125.00 150.00   62
 71  \w     57.00  83.00   0.50    0.49    --  113.25-125.00 120.00   52
 72  \w     79.00 106.00   0.50    0.49    --  113.25 -94.00 120.00   54
 73  \w     52.00  77.00   0.50    0.49    --  113.25 -94.00 120.00   50
 74  \w     42.00  74.00   0.50    0.49    --  113.25 -94.00   0.00   64
 75  \w     79.00 106.00   0.50    0.49    --  113.25 -94.00   0.00   54
 76  \w     75.00 105.00   0.50    0.49    --  113.25 -94.00  60.00   60
 77  \w     73.00 106.00   0.50    0.49    --  113.25 -94.00  30.00   66
 78  \w     50.00  92.00   0.50    0.49    --  113.25 -94.00 -30.00   84
 79  \w     72.00 106.00   0.50    0.49    --  113.25 -94.00 -60.00   68
 80  \w     64.00 106.00   0.50    0.49    --  113.25 -94.00-120.00   84
 81  \w     75.00 106.00   0.50    0.49    --  113.25 -94.00-180.00   62
 82  \w    100.00 140.00   0.50    0.49    --  113.25 -88.00-129.94   80
 83  \w     42.00  69.00   0.50    0.49    --  113.25 -88.00-129.94   54
 84  \w     47.00  72.00   0.50    0.49    --  113.25 -94.00  60.00   50
 85  \w     74.00 105.00   0.50    0.49    --  113.25 -94.00  90.00   62
 86  \w     45.00  88.00   0.50    0.49    --  113.25 -94.00 150.00   86
 87  \w     42.00  68.00   0.50    0.49    --  113.25 -88.00 122.73   52
 88  \w     48.00  74.00   0.50    0.49    --  113.25 -86.00 165.16   52
 89  \w    109.00 135.00   0.50    0.49    --  113.25 -86.00 165.16   52
 90  \w     83.00 115.00   0.50    0.49    --  113.25 -88.00 122.73   64
 91  \w     43.00  72.00   0.50    0.49    --  113.25 -83.00 -25.48   58
 92  \w    112.00 138.00   0.50    0.49    --  113.25 -83.00 -25.48   52
 93  \w    106.00 141.00   0.50    0.49    --  113.25 -88.00 -64.03   70
 94  \w     45.00  94.00   0.50    0.49    --  113.25 -88.00 -77.70   98
 95  \w     42.00  71.00   0.50    0.49    --  113.25 -82.00-164.90   58
 96  \w   -113.00 -36.00   0.50    0.12    --  -48.06 -42.00 105.66  154
 97  \w   -121.00 -36.00   0.50    0.12    --  -48.06 -37.00  30.00  170
 98  \w    -51.00 -25.00   0.50    0.49    --  -91.75  45.00  60.00   52
 99  \w    -78.00 -38.00   0.50    0.49    --  -91.75  77.00  60.00   80
100  \w    -69.00 -23.00   0.50    0.12    --  -48.06 125.00-180.00   92
;
_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      -0.1465252000
_diffrn_orient_matrix_UB_12      -0.0014937000
_diffrn_orient_matrix_UB_13      0.0188350000
_diffrn_orient_matrix_UB_21      0.0321819000
_diffrn_orient_matrix_UB_22      0.0035737000
_diffrn_orient_matrix_UB_23      0.0853695000
_diffrn_orient_matrix_UB_31      -0.0032367000
_diffrn_orient_matrix_UB_32      0.1024253000
_diffrn_orient_matrix_UB_33      -0.0027195000
_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  0.0400
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            63925
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.060
_diffrn_reflns_theta_min         3.867
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.592
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.345
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.033
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_preparation
'crystallization from concentrated cooled hexane solution.'
_exptl_crystal_recrystallization_method
'crystallization from concentrated cooled hexane solution.'
_exptl_crystal_size_max          0.252
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.098
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2529 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0034(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         5902
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0260
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0380P)^2^+0.6975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0680
_refine_ls_wR_factor_ref         0.0682
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                5837
_reflns_number_total             5902
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla25059_refinalized
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_database_code               1573276
_chemical_oxdiff_formula         'Sc Si3 C15 H15 N2'
_chemical_oxdiff_usercomment     'sc tmeda'
_shelx_estimated_absorpt_t_max   0.720
_shelx_estimated_absorpt_t_min   0.465
_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. Others
 Fixed Sof: C19(0.3) H19A(0.3) H19B(0.3) C18(0.3) H18A(0.3) H18B(0.3) C20(0.7)
 H20A(0.7) H20B(0.7) C17(0.7) H17A(0.7) H17B(0.7)
3.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C18(H18A,H18B), C20(H20A,H20B), C17(H17A,H17B)
3.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C16(H16A,H16B,H16C), C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C11(H11A,H11B,H11C),
 C15(H15A,H15B,H15C), C13(H13A,H13B,H13C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C),
  C12(H12A,H12B,H12C)
;
_shelx_res_checksum              74081
_shelx_hkl_checksum              76909
_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 1.325
_oxdiff_exptl_absorpt_empirical_full_min 0.847