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_1573277
_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 Lu N2 Si3'
_chemical_formula_sum            'C18 H49 Lu N2 Si3'
_chemical_formula_weight         552.83
_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                   9.76140(10)
_cell_length_b                   16.1956(2)
_cell_length_c                   17.1923(2)
_cell_measurement_reflns_used    43755
_cell_measurement_temperature    99.97(11)
_cell_measurement_theta_max      79.5750
_cell_measurement_theta_min      3.7760
_cell_volume                     2717.96(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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      99.97(11)
_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 0.999
_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    -10.00  20.00   0.50    0.11    --  -47.94  19.00  90.00   60
  2  \w    -62.00  20.00   0.50    0.11    --  -47.94  57.00  60.00  164
  3  \w    -12.00  20.00   0.50    0.11    --  -47.94  19.00   0.00   64
  4  \w    -16.00  28.00   0.50    0.11    --  -47.94  19.00  60.00   88
  5  \w    -12.00  28.00   0.50    0.11    --  -47.94  19.00  30.00   80
  6  \w    -12.00  23.00   0.50    0.11    --  -47.94  19.00 -30.00   70
  7  \w    -14.00  27.00   0.50    0.11    --  -47.94  19.00 -60.00   82
  8  \w    -15.00  28.00   0.50    0.11    --  -47.94  19.00-180.00   86
  9  \w     42.00  69.00   0.50    0.43    --  113.25 -61.00-150.00   54
 10  \w     47.00  89.00   0.50    0.43    --  113.25 -77.00-120.00   84
 11  \w     62.00  88.00   0.50    0.43    --  113.25 -77.00 -60.00   52
 12  \w     53.00  79.00   0.50    0.43    --  113.25 -77.00-150.00   52
 13  \w     45.00  75.00   0.50    0.43    --  113.25 -77.00   0.00   60
 14  \w     74.00 100.00   0.50    0.43    --  113.25 -77.00  60.00   52
 15  \w     42.00  73.00   0.50    0.43    --  113.25 -77.00  60.00   62
 16  \w     44.00  70.00   0.50    0.43    --  113.25 -61.00 150.00   52
 17  \w     44.00  70.00   0.50    0.43    --  113.25 -77.00 150.00   52
 18  \w     42.00  67.00   0.50    0.43    --  113.25 -61.00  60.00   50
 19  \w     43.00  69.00   0.50    0.43    --  113.25 -61.00 -90.00   52
 20  \w     45.00  70.00   0.50    0.43    --  113.25 -61.00-180.00   50
 21  \w     38.00  82.00   0.50    0.11    --   47.94-125.00-150.00   88
 22  \w     57.00  91.00   0.50    0.43    --  113.25-125.00-180.00   68
 23  \w     48.00  93.00   0.50    0.43    --  113.25-125.00-120.00   90
 24  \w     64.00  95.00   0.50    0.43    --  113.25-125.00   0.00   62
 25  \w     86.00 111.00   0.50    0.43    --  113.25-125.00  30.00   50
 26  \w     47.00  79.00   0.50    0.43    --  113.25-125.00  60.00   64
 27  \w     47.00  72.00   0.50    0.43    --  113.25-125.00  30.00   50
 28  \w     44.00  74.00   0.50    0.43    --  113.25-106.00 171.86   60
 29  \w     81.00 108.00   0.50    0.43    --  113.25-106.00 171.86   54
 30  \w     50.00 107.00   0.50    0.43    --  113.25-104.00  72.75  114
 31  \w     75.00 106.00   0.50    0.43    --  113.25 -99.00 -42.96   62
 32  \w     81.00 106.00   0.50    0.43    --  113.25 -99.00  -4.84   50
 33  \w     43.00  76.00   0.50    0.43    --  113.25 -99.00  -4.84   66
 34  \w     50.00  76.00   0.50    0.43    --  113.25 -94.00   0.00   52
 35  \w      5.00  72.00   0.50    0.11    --   47.94 -99.00-120.00  134
 36  \w     48.00  74.00   0.50    0.43    --  113.25-101.00-175.03   52
 37  \w     76.00 106.00   0.50    0.43    --  113.25-101.00-175.03   60
 38  \w     66.00 106.00   0.50    0.43    --  113.25 -98.00-159.53   80
 39  \w     51.00  76.00   0.50    0.43    --  113.25 -94.00-120.00   50
 40  \w     80.00 105.00   0.50    0.43    --  113.25 -94.00-150.00   50
 41  \w     67.00 100.00   0.50    0.43    --  113.25 -94.00 -90.00   66
 42  \w     57.00  82.00   0.50    0.43    --  113.25 -94.00 -60.00   50
 43  \w     80.00 106.00   0.50    0.43    --  113.25 -94.00   0.00   52
 44  \w     69.00 102.00   0.50    0.43    --  113.25 -94.00 150.00   66
 45  \w     56.00  85.00   0.50    0.43    --  113.25 -94.00 120.00   58
 46  \w     46.00  74.00   0.50    0.43    --  113.25 -88.00 103.09   56
 47  \w     64.00 106.00   0.50    0.43    --  113.25 -94.00  90.00   84
 48  \w     52.00  99.00   0.50    0.43    --  113.25 -94.00  60.00   94
 49  \w     68.00 102.00   0.50    0.43    --  113.25 -94.00  30.00   68
 50  \w     87.00 113.00   0.50    0.43    --  113.25 -88.00 103.09   52
 51  \w     55.00  81.00   0.50    0.43    --  113.25 -86.00  74.96   52
 52  \w     86.00 112.00   0.50    0.43    --  113.25 -86.00  74.96   52
 53  \w     86.00 112.00   0.50    0.43    --  113.25 -86.00-103.00   52
 54  \w     63.00 113.00   0.50    0.43    --  113.25 -87.00-137.07  100
 55  \w     81.00 106.00   0.50    0.43    --  113.25 -94.00-120.00   50
 56  \w    101.00 138.00   0.50    0.43    --  113.25 -82.00-174.80   74
 57  \w     42.00  69.00   0.50    0.43    --  113.25 -82.00-174.80   54
 58  \w     48.00  74.00   0.50    0.43    --  113.25 -86.00-103.00   52
 59  \w     99.00 125.00   0.50    0.43    --  113.25 -82.00 -42.58   52
 60  \w     95.00 137.00   0.50    0.43    --  113.25 -85.00  41.42   84
 61  \w     42.00  81.00   0.50    0.43    --  113.25 -85.00  41.42   78
 62  \w    114.00 162.00   0.50    0.43    --  113.25  15.00 120.00   96
 63  \w    107.00 138.00   0.50    0.43    --  113.25  61.00  60.00   62
 64  \w    111.00 137.00   0.50    0.43    --  113.25  77.00 -60.00   52
 65  \w    140.00 167.00   0.50    0.43    --  113.25  77.00 -60.00   54
 66  \w    114.00 140.00   0.50    0.43    --  113.25  61.00 -60.00   52
 67  \w    120.00 162.00   0.50    0.43    --  113.25  61.00 -90.00   84
 68  \w    115.00 178.00   0.50    0.43    --  113.25  45.00-120.00  126
 69  \w    102.00 154.00   0.50    0.43    --  113.25  45.00 -90.00  104
 70  \w    104.00 170.00   0.50    0.43    --  113.25  45.00 -60.00  132
 71  \w    122.00 155.00   0.50    0.43    --  113.25  45.00 -30.00   66
 72  \w    141.00 178.00   0.50    0.43    --  113.25  45.00   0.00   74
 73  \w    104.00 129.00   0.50    0.43    --  113.25  45.00  30.00   50
 74  \w    117.00 154.00   0.50    0.43    --  113.25  30.00  60.00   74
 75  \w    108.00 138.00   0.50    0.43    --  113.25  45.00   0.00   60
 76  \w    110.00 135.00   0.50    0.43    --  113.25  30.00 -30.00   50
 77  \w    134.00 172.00   0.50    0.43    --  113.25  15.00  30.00   76
 78  \w    100.00 148.00   0.50    0.43    --  113.25  15.00 -90.00   96
 79  \w    100.00 130.00   0.50    0.43    --  113.25  15.00-120.00   60
 80  \w    115.00 140.00   0.50    0.43    --  113.25  30.00-150.00   50
 81  \w    109.00 141.00   0.50    0.43    --  113.25  30.00-180.00   64
 82  \w    107.00 161.00   0.50    0.43    --  113.25  15.00-180.00  108
 83  \w    142.00 168.00   0.50    0.43    --  113.25  15.00-120.00   52
 84  \w    101.00 131.00   0.50    0.43    --  113.25  15.00  60.00   60
 85  \w    141.00 168.00   0.50    0.43    --  113.25  15.00  60.00   54
 86  \w    140.00 166.00   0.50    0.43    --  113.25 125.00 120.00   52
 87  \w    143.00 169.00   0.50    0.43    --  113.25 125.00  60.00   52
 88  \w    140.00 165.00   0.50    0.43    --  113.25 125.00  30.00   50
 89  \w    102.00 135.00   0.50    0.43    --  113.25 125.00  30.00   66
 90  \w    129.00 155.00   0.50    0.43    --  113.25 125.00 -60.00   52
 91  \w    109.00 172.00   0.50    0.43    --  113.25 111.00-106.89  126
 92  \w    -49.00 -23.00   0.50    0.43    --  -91.75  45.00   0.00   52
 93  \w   -118.00 -92.00   0.50    0.43    --  -91.75 -49.00 146.85   52
 94  \w    -86.00 -58.00   0.50    0.11    --  -47.94 125.00-180.00   56
;
_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      0.1268198000
_diffrn_orient_matrix_UB_12      -0.0508746000
_diffrn_orient_matrix_UB_13      -0.0235512000
_diffrn_orient_matrix_UB_21      0.0678017000
_diffrn_orient_matrix_UB_22      0.0205545000
_diffrn_orient_matrix_UB_23      0.0785803000
_diffrn_orient_matrix_UB_31      -0.0648890000
_diffrn_orient_matrix_UB_32      -0.0777521000
_diffrn_orient_matrix_UB_33      0.0360347000
_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  0.0884
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            59230
_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         79.906
_diffrn_reflns_theta_min         3.750
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.228
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64341
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.351
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_preparation
'crystallization from cold ether/hexane mixture.'
_exptl_crystal_recrystallization_method hexane
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.220
_refine_diff_density_min         -1.299
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 2439 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.035(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         5898
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0264P)^2^+18.3519P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0907
_refine_ls_wR_factor_ref         0.0909
_reflns_Friedel_coverage         0.768
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                5793
_reflns_number_total             5898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla23157_auto
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_database_code               1573277
_chemical_oxdiff_formula         'Lu Si4 C10 H10 O5'
_chemical_oxdiff_usercomment     ELTA-162
_shelx_estimated_absorpt_t_max   0.684
_shelx_estimated_absorpt_t_min   0.438
_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:
 C15(H15A,H15B), C1(H1A,H1B), C16(H16A,H16B)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C),
 C11(H11A,H11B,H11C), C18(H18A,H18B,H18C), C10(H10A,H10B,H10C), C12(H12A,H12B,
 H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C8(H8A,H8B,H8C)
;
_shelx_res_checksum              12123
_shelx_hkl_checksum              90626
_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 1.519
_oxdiff_exptl_absorpt_empirical_full_min 0.544