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_1573275
_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         '1(C18 H47 Lu O3 Si3)'
_chemical_formula_sum            'C18 H47 Lu O3 Si3'
_chemical_formula_weight         570.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-08-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-09-04 deposited with the CCDC.	2024-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.1660(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.06420(10)
_cell_length_b                   15.98610(10)
_cell_length_c                   19.10330(10)
_cell_measurement_reflns_used    78258
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.5130
_cell_measurement_theta_min      3.6620
_cell_volume                     5562.62(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.112a 64-bit (release 01-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.112a (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    'XS  (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 0.993
_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     44.00 111.00   0.50    0.23    --  113.25-125.00 150.00  134
  2  \w     45.00  70.00   0.50    0.23    --  113.25-125.00  90.00   50
  3  \w     52.00  77.00   0.50    0.23    --  113.25-125.00 120.00   50
  4  \w     79.00 105.00   0.50    0.23    --  113.25-125.00  90.00   52
  5  \w     75.00 111.00   0.50    0.23    --  113.25-125.00  30.00   72
  6  \w     53.00  78.00   0.50    0.23    --  113.25-125.00   0.00   50
  7  \w     45.00  72.00   0.50    0.23    --  113.25 -94.00   0.00   54
  8  \w     78.00 106.00   0.50    0.23    --  113.25 -94.00   0.00   56
  9  \w     61.00 104.00   0.50    0.23    --  113.25 -94.00 -90.00   86
 10  \w     77.00 106.00   0.50    0.23    --  113.25 -94.00-150.00   58
 11  \w     44.00  76.00   0.50    0.23    --  113.25-125.00-180.00   64
 12  \w     77.00 103.00   0.50    0.23    --  113.25-125.00-150.00   52
 13  \w     44.00 104.00   0.50    0.23    --  113.25 -94.00-120.00  120
 14  \w     42.00 106.00   0.50    0.23    --  113.25 -94.00 -60.00  128
 15  \w     81.00 106.00   0.50    0.23    --  113.25 -94.00  30.00   50
 16  \w     72.00 106.00   0.50    0.23    --  113.25 -94.00  60.00   68
 17  \w     67.00 106.00   0.50    0.23    --  113.25 -94.00 120.00   78
 18  \w     80.00 105.00   0.50    0.23    --  113.25 -94.00 150.00   50
 19  \w     72.00 112.00   0.50    0.23    --  113.25 -82.00 137.46   80
 20  \w     54.00  80.00   0.50    0.23    --  113.25 -94.00  30.00   52
 21  \w     95.00 123.00   0.50    0.23    --  113.25 -84.00-132.81   56
 22  \w    106.00 137.00   0.50    0.23    --  113.25 -78.00 -66.12   62
 23  \w     49.00  75.00   0.50    0.23    --  113.25 -77.00-150.00   52
 24  \w     50.00  88.00   0.50    0.23    --  113.25 -78.00 -66.12   76
 25  \w     61.00  87.00   0.50    0.23    --  113.25 -77.00-120.00   52
 26  \w     47.00  73.00   0.50    0.23    --  113.25 -77.00 -30.00   52
 27  \w     42.00  88.00   0.50    0.23    --  113.25 -77.00  60.00   92
 28  \w     47.00  77.00   0.50    0.23    --  113.25 -77.00 120.00   60
 29  \w     42.00  70.00   0.50    0.23    --  113.25 -77.00 150.00   56
 30  \w     86.00 112.00   0.50    0.23    --  113.25 -77.00 150.00   52
 31  \w     95.00 135.00   0.50    0.23    --  113.25 -75.00 165.38   80
 32  \w     86.00 129.00   0.50    0.23    --  113.25 -75.00 -28.03   86
 33  \w     45.00  70.00   0.50    0.23    --  113.25 -61.00  60.00   50
 34  \w     42.00  67.00   0.50    0.23    --  113.25 -61.00  90.00   50
 35  \w     43.00  71.00   0.50    0.23    --  113.25 -61.00 -60.00   56
 36  \w     43.00  71.00   0.50    0.23    --  113.25 -61.00-120.00   56
 37  \w     43.00  71.00   0.50    0.23    --  113.25 -61.00-180.00   56
 38  \w    143.00 178.00   0.50    0.23    --  113.25 125.00-120.00   70
 39  \w    141.00 177.00   0.50    0.23    --  113.25 125.00 -60.00   72
 40  \w    103.00 162.00   0.50    0.23    --  113.25 125.00   0.00  118
 41  \w     97.00 129.00   0.50    0.23    --  113.25 125.00 150.00   64
 42  \w    134.00 164.00   0.50    0.23    --  113.25 125.00 150.00   60
 43  \w    110.00 178.00   0.50    0.23    --  113.25  77.00 150.00  136
 44  \w    152.00 178.00   0.50    0.23    --  113.25  77.00  30.00   52
 45  \w    147.00 178.00   0.50    0.23    --  113.25  77.00 -30.00   62
 46  \w    112.00 137.00   0.50    0.23    --  113.25  77.00 -30.00   50
 47  \w    116.00 148.00   0.50    0.23    --  113.25  61.00 -90.00   64
 48  \w    113.00 138.00   0.50    0.23    --  113.25  77.00-120.00   50
 49  \w    110.00 136.00   0.50    0.23    --  113.25  61.00-120.00   52
 50  \w    112.00 140.00   0.50    0.23    --  113.25  61.00-180.00   56
 51  \w    153.00 178.00   0.50    0.23    --  113.25  61.00-180.00   50
 52  \w    102.00 149.00   0.50    0.23    --  113.25  45.00-180.00   94
 53  \w    149.00 178.00   0.50    0.23    --  113.25  61.00-120.00   58
 54  \w    105.00 177.00   0.50    0.23    --  113.25  45.00 -60.00  144
 55  \w    107.00 133.00   0.50    0.23    --  113.25  61.00   0.00   52
 56  \w    151.00 177.00   0.50    0.23    --  113.25  45.00 -30.00   52
 57  \w    139.00 177.00   0.50    0.23    --  113.25  61.00   0.00   76
 58  \w    104.00 145.00   0.50    0.23    --  113.25  45.00 -30.00   82
 59  \w    118.00 165.00   0.50    0.23    --  113.25  45.00  60.00   94
 60  \w    114.00 139.00   0.50    0.23    --  113.25  30.00 120.00   50
 61  \w    130.00 176.00   0.50    0.23    --  113.25  45.00 150.00   92
 62  \w    123.00 149.00   0.50    0.23    --  113.25  45.00 120.00   52
 63  \w    112.00 137.00   0.50    0.23    --  113.25  45.00  90.00   50
 64  \w    115.00 159.00   0.50    0.23    --  113.25  15.00 -30.00   88
 65  \w    141.00 171.00   0.50    0.23    --  113.25  15.00 -90.00   60
 66  \w    127.00 171.00   0.50    0.23    --  113.25  15.00-120.00   88
 67  \w     34.00  94.00   0.50    0.06    --   47.94-125.00 -60.00  120
 68  \w      0.00  80.00   0.50    0.06    --   47.94 -99.00-180.00  160
 69  \w      0.00  80.00   0.50    0.06    --   47.94 -99.00-180.00  160
 70  \w    -63.00  25.00   0.50    0.06    --  -47.94  57.00-180.00  176
 71  \w    -63.00  25.00   0.50    0.06    --  -47.94  57.00-180.00  176
 72  \w    -16.00  28.00   0.50    0.06    --  -47.94  19.00-180.00   88
 73  \w    -16.00  28.00   0.50    0.06    --  -47.94  19.00 -30.00   88
 74  \w    -16.00  28.00   0.50    0.06    --  -47.94  19.00 -60.00   88
 75  \w    -16.00  28.00   0.50    0.06    --  -47.94  19.00   0.00   88
 76  \w    -63.00  25.00   0.50    0.06    --  -47.94  57.00  60.00  176
 77  \w    -63.00  25.00   0.50    0.06    --  -47.94  57.00  60.00  176
 78  \w   -120.00 -35.00   0.50    0.06    --  -47.94 -42.00  43.67  170
 79  \w   -163.00-106.00   0.50    0.23    --  -91.75 -61.00 120.00  114
 80  \w   -163.00 -93.00   0.50    0.23    --  -91.75 -50.00-123.97  140
;
_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      0.0431711000
_diffrn_orient_matrix_UB_12      0.0038219000
_diffrn_orient_matrix_UB_13      0.0820305000
_diffrn_orient_matrix_UB_21      -0.0701499000
_diffrn_orient_matrix_UB_22      -0.0232198000
_diffrn_orient_matrix_UB_23      0.0199395000
_diffrn_orient_matrix_UB_31      0.0191941000
_diffrn_orient_matrix_UB_32      -0.0934324000
_diffrn_orient_matrix_UB_33      -0.0016159000
_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  0.0494
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            123523
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.199
_diffrn_reflns_theta_min         2.877
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.122
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.586
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.112a (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_density_diffrn    1.363
_exptl_crystal_description       prism
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.127
_refine_diff_density_max         1.810
_refine_diff_density_min         -1.855
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         12072
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0338
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0437P)^2^+10.5226P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11204
_reflns_number_total             12072
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla24028_refinalized
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_original_cell_volume        5562.61(6)
_cod_database_code               1573275
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Lu Si3 C20 H20 O3'
_chemical_oxdiff_usercomment     ET-253
_shelx_estimated_absorpt_t_max   0.425
_shelx_estimated_absorpt_t_min   0.240
_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
C38 \\sim C40: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
Si7 \\sim Si9 \\sim Si6 \\sim Si8: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Si9 \\sim Si8: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
Uanis(C45) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(Si1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(Si6)=Sof(Si8)=Sof(Si4)=Sof(O7)=Sof(O9)=Sof(O8)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C19)=
 Sof(H19A)=Sof(H19B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C33)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C32)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(C48)=
 Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(1)
 Sof(Si7)=Sof(Si9)=Sof(Si5)=Sof(O4)=Sof(O6)=Sof(O5)=Sof(C24)=Sof(H24A)=
 Sof(H24B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C20)=Sof(H20A)=
 Sof(H20B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C34)=Sof(H34A)=Sof(H34B)=
 Sof(H34C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C50)=Sof(H50A)=Sof(H50B)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C53(H53A,H53B), C22(H22A,H22B), C51(H51A,H51B), C20(H20A,
 H20B), C50(H50A,H50B), C52(H52A,H52B), C23(H23A,H23B), C21(H21A,H21B),
 C44(H44A,H44B), C19(H19A,H19B), C46(H46A,H46B), C45(H45A,H45B), C47(H47A,H47B),
  C15(H15A,H15B), C14(H14A,H14B), C16(H16A,H16B), C1(H1A,H1B), C3(H3A,H3B),
 C17(H17A,H17B), C2(H2A,H2B)
4.b Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C41(H41A,H41B,H41C), C36(H36A,H36B,H36C), C54(H54A,H54B,
 H54C), C34(H34A,H34B,H34C), C30(H30A,H30B,H30C), C28(H28A,H28B,H28C), C49(H49A,
 H49B,H49C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C), C29(H29A,H29B,H29C),
 C40(H40A,H40B,H40C), C43(H43A,H43B,H43C), C27(H27A,H27B,H27C), C33(H33A,H33B,
 H33C), C26(H26A,H26B,H26C), C32(H32A,H32B,H32C), C37(H37A,H37B,H37C), C25(H25A,
 H25B,H25C), C31(H31A,H31B,H31C), C48(H48A,H48B,H48C), C39(H39A,H39B,H39C),
 C5(H5A,H5B,H5C), C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C7(H7A,H7B,H7C),
 C4(H4A,H4B,H4C), C18(H18A,H18B,H18C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C13(H13A,H13B,H13C), C8(H8A,H8B,H8C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              45970
_shelx_hkl_checksum              32495
_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 1.871
_oxdiff_exptl_absorpt_empirical_full_min 0.659