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_1573282
_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         'C22 H57 Lu O P2 Si3'
_chemical_formula_sum            'C22 H57 Lu O P2 Si3'
_chemical_formula_weight         658.85
_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             2024-04-18
_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                   10.49690(10)
_cell_length_b                   18.04320(10)
_cell_length_c                   18.05330(10)
_cell_measurement_reflns_used    151506
_cell_measurement_temperature    99.98(13)
_cell_measurement_theta_max      79.4610
_cell_measurement_theta_min      4.8240
_cell_volume                     3419.25(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(13)
_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 0.994
_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    -86.00 -16.00   0.50    0.20    --  -47.69 125.00  90.00  140
  2  \w    -63.00  25.00   0.50    0.20    --  -47.69  57.00-150.00  176
  3  \w    -16.00  28.00   0.50    0.20    --  -47.69  19.00 -90.00   88
  4  \w    -42.00  26.00   0.50    0.20    --  -47.69  37.00 -30.00  136
  5  \w    -16.00  28.00   0.50    0.20    --  -47.69  19.00  60.00   88
  6  \w    -70.00  16.00   0.50    0.20    --  -47.69  77.00 -30.00  172
  7  \w    -42.00  26.00   0.50    0.20    --  -47.69  37.00  90.00  136
  8  \w    -42.00  26.00   0.50    0.20    --  -47.69  37.00-150.00  136
  9  \w    -86.00 -16.00   0.50    0.20    --  -47.69 125.00 150.00  140
 10  \w    -27.00   8.00   0.50    0.20    --   47.69 -19.00 120.00   70
 11  \w   -163.00-106.00   0.50    0.81    --  -91.75 -61.00 -30.00  114
 12  \w    101.00 178.00   0.50    0.81    --  113.25  30.00-120.00  154
 13  \w    101.00 178.00   0.50    0.81    --  113.25  30.00 -90.00  154
 14  \w     42.00 135.00   0.50    0.81    --  113.25 -75.00 171.92  186
 15  \w    100.00 172.00   0.50    0.81    --  113.25  15.00-180.00  144
 16  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00 -30.00  128
 17  \w     42.00 139.00   0.50    0.81    --  113.25 -83.00-176.30  194
 18  \w     42.00  87.00   0.50    0.81    --  113.25 -68.00-176.67   90
 19  \w     42.00  71.00   0.50    0.81    --  113.25 -61.00-120.00   58
 20  \w    110.00 178.00   0.50    0.81    --  113.25  77.00  30.00  136
 21  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00   0.00  188
 22  \w    100.00 172.00   0.50    0.81    --  113.25  15.00-150.00  144
 23  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00-180.00  128
 24  \w     95.00 178.00   0.50    0.81    --  113.25 125.00-120.00  166
 25  \w    101.00 178.00   0.50    0.81    --  113.25  30.00   0.00  154
 26  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00  30.00  128
 27  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00-120.00  188
 28  \w     44.00 111.00   0.50    0.81    --  113.25-125.00-120.00  134
 29  \w    101.00 178.00   0.50    0.81    --  113.25  38.00  50.19  154
 30  \w    108.00 178.00   0.50    0.81    --  113.25  92.00 112.05  140
 31  \w     42.00 135.00   0.50    0.81    --  113.25 -75.00 178.77  186
 32  \w     42.00 135.00   0.50    0.81    --  113.25 -75.00 -71.04  186
 33  \w    106.00 178.00   0.50    0.81    --  113.25  61.00-150.00  144
 34  \w     44.00 111.00   0.50    0.81    --  113.25-125.00  90.00  134
 35  \w     42.00  71.00   0.50    0.81    --  113.25 -61.00 120.00   58
 36  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00  60.00  128
 37  \w    100.00 172.00   0.50    0.81    --  113.25  15.00  60.00  144
 38  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00 -90.00  128
 39  \w    101.00 178.00   0.50    0.81    --  113.25  45.00-150.00  154
 40  \w    106.00 178.00   0.50    0.81    --  113.25  61.00 -90.00  144
 41  \w    101.00 178.00   0.50    0.81    --  113.25  45.00   0.00  154
 42  \w     44.00 111.00   0.50    0.81    --  113.25-125.00 -90.00  134
 43  \w    101.00 178.00   0.50    0.81    --  113.25  30.00 -30.00  154
 44  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00   0.00  128
 45  \w     42.00  71.00   0.50    0.81    --  113.25 -61.00  60.00   58
 46  \w    110.00 178.00   0.50    0.81    --  113.25  77.00  90.00  136
 47  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00-120.00  128
 48  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00 120.00  128
 49  \w    101.00 178.00   0.50    0.81    --  113.25  30.00  90.00  154
 50  \w    110.00 178.00   0.50    0.81    --  113.25  77.00-150.00  136
 51  \w    107.00 178.00   0.50    0.81    --  113.25  97.00 103.02  142
 52  \w     42.00  71.00   0.50    0.81    --  113.25 -61.00 -60.00   58
 53  \w     95.00 178.00   0.50    0.81    --  113.25 125.00 150.00  166
 54  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00  30.00  188
 55  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00 150.00  128
 56  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00  90.00  188
 57  \w    101.00 178.00   0.50    0.81    --  113.25  30.00 -60.00  154
 58  \w    106.00 178.00   0.50    0.81    --  113.25  61.00 -60.00  144
 59  \w    101.00 178.00   0.50    0.81    --  113.25  45.00 150.00  154
 60  \w     44.00 111.00   0.50    0.81    --  113.25-125.00 -30.00  134
 61  \w     44.00 111.00   0.50    0.81    --  113.25-125.00   0.00  134
 62  \w     44.00 111.00   0.50    0.81    --  113.25-125.00  60.00  134
 63  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00 -60.00  128
 64  \w    110.00 178.00   0.50    0.81    --  113.25  77.00 -30.00  136
 65  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00 150.00  188
 66  \w    106.00 178.00   0.50    0.81    --  113.25  61.00-120.00  144
 67  \w     95.00 178.00   0.50    0.81    --  113.25 125.00 -90.00  166
 68  \w     95.00 178.00   0.50    0.81    --  113.25 125.00  90.00  166
 69  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00 -60.00  188
 70  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00-150.00  128
 71  \w     42.00 106.00   0.50    0.81    --  113.25 -94.00  90.00  128
 72  \w     44.00 111.00   0.50    0.81    --  113.25-125.00-180.00  134
 73  \w     42.00  71.00   0.50    0.81    --  113.25 -61.00 -30.00   58
 74  \w    106.00 178.00   0.50    0.81    --  113.25  61.00 120.00  144
 75  \w    101.00 178.00   0.50    0.81    --  113.25  45.00-180.00  154
 76  \w    101.00 178.00   0.50    0.81    --  113.25  45.00  60.00  154
 77  \w    101.00 178.00   0.50    0.81    --  113.25  45.00 120.00  154
 78  \w    101.00 178.00   0.50    0.81    --  113.25  30.00-150.00  154
 79  \w     42.00 141.00   0.50    0.81    --  113.25 -88.00  62.20  198
 80  \w    101.00 178.00   0.50    0.81    --  113.25  30.00  60.00  154
 81  \w     95.00 178.00   0.50    0.81    --  113.25 125.00 -30.00  166
 82  \w     95.00 178.00   0.50    0.81    --  113.25 125.00  30.00  166
 83  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00-150.00  188
 84  \w     42.00 136.00   0.50    0.81    --  113.25 -77.00 120.00  188
 85  \w   -119.00 -35.00   0.50    0.20    --  -47.69 -45.00-144.37  168
 86  \w   -119.00 -35.00   0.50    0.20    --  -47.69 -46.00  14.35  168
 87  \w   -119.00 -35.00   0.50    0.20    --  -47.69 -46.00 -24.28  168
 88  \w   -120.00 -35.00   0.50    0.20    --  -47.69 -44.00-104.91  170
 89  \w   -119.00 -35.00   0.50    0.20    --  -47.69 -46.00 -51.46  168
 90  \w   -119.00 -35.00   0.50    0.20    --  -47.69 -46.00 139.31  168
 91  \w   -120.00 -35.00   0.50    0.20    --  -47.69 -43.00  90.82  170
 92  \w   -120.00 -35.00   0.50    0.20    --  -47.69 -42.00  47.56  170
 93  \w   -120.00 -35.00   0.50    0.20    --  -47.69 -44.00-176.06  170
 94  \w     35.00 119.00   0.50    0.20    --   47.69  47.00-174.26  168
 95  \w     35.00 119.00   0.50    0.20    --   47.69  45.00  -1.51  168
 96  \w     35.00 119.00   0.50    0.20    --   47.69  47.00 -80.93  168
 97  \w   -163.00 -89.00   0.50    0.81    --  -91.75 -45.00  47.26  148
 98  \w   -163.00 -82.00   0.50    0.81    --  -91.75 -47.00 -12.19  162
 99  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00 -60.00  168
100  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00-120.00  168
101  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -46.00  17.79  168
102  \w   -164.00 -78.00   0.50    0.81    --  -91.75 -44.00 106.18  172
103  \w   -164.00 -78.00   0.50    0.81    --  -91.75 -43.00-167.16  172
104  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00 150.00  168
105  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -46.00 -81.52  168
106  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00 165.20  168
107  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -46.00  38.47  168
108  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00 -30.00  168
109  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00  62.13  168
110  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00  90.00  168
111  \w   -164.00 -78.00   0.50    0.81    --  -91.75 -44.00-140.74  172
112  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00  80.81  168
113  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -46.00 137.54  168
114  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00-103.31  168
115  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00-180.00  168
116  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00 -40.91  168
117  \w   -163.00 -79.00   0.50    0.81    --  -91.75 -45.00   0.00  168
118  \w     99.00 178.00   0.50    0.81    --  113.25  53.00 148.17  158
119  \w    101.00 178.00   0.50    0.81    --  113.25  45.00  30.00  154
120  \w    101.00 178.00   0.50    0.81    --  113.25  45.00  90.00  154
121  \w    101.00 178.00   0.50    0.81    --  113.25  45.00 -60.00  154
122  \w    101.00 178.00   0.50    0.81    --  113.25  45.00-120.00  154
123  \w    106.00 178.00   0.50    0.81    --  113.25  61.00-180.00  144
;
_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      -0.1156139000
_diffrn_orient_matrix_UB_12      -0.0081693000
_diffrn_orient_matrix_UB_13      -0.0517704000
_diffrn_orient_matrix_UB_21      -0.0587237000
_diffrn_orient_matrix_UB_22      0.0709977000
_diffrn_orient_matrix_UB_23      0.0329739000
_diffrn_orient_matrix_UB_31      0.0685906000
_diffrn_orient_matrix_UB_32      0.0467434000
_diffrn_orient_matrix_UB_33      -0.0593201000
_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  0.0879
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 1.000
_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       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            229465
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.650
_diffrn_reflns_theta_min         3.463
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.486
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.425
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
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    1.280
_exptl_crystal_description       prism
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.153
_refine_diff_density_min         -0.648
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Flack x determined using 3202 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.030(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         7472
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0516P)^2^+2.9340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0820
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                7317
_reflns_number_total             7472
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05983b2.cif
_cod_data_source_block           pla23105_refinalized
_cod_depositor_comments
'Adding full bibliography for 1573273--1573282.cif.'
_cod_database_code               1573282
_chemical_oxdiff_formula         'Lu C50 H50 P2 O Si3'
_chemical_oxdiff_usercomment     ELTA98_clear_colorless_prism
_shelx_estimated_absorpt_t_max   0.586
_shelx_estimated_absorpt_t_min   0.278
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
2. Others
 Fixed Sof: C1(0.5) H1A(0.5) H1B(0.5) C2(0.5) H2A(0.5) H2B(0.5) C3(0.5)
 H3A(0.5) H3B(0.5) C5(0.5) H5A(0.5) H5B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C008(H00A,H00B), C00A(H00F,H00G), C00B(H00H,H00I), C00C(H00J,H00K), C00J(H00,
 HC), C00R(H7,HP), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C4(H4A,
 H4B)
3.b Idealised Me refined as rotating group:
 C009(H00C,H00D,H00E), C00D(H00L,H00M,H00N), C00E(H00O,H00P,H00Q), C00F(H00R,
 H00S,H00T), C00G(H00U,H00V,H00W), C00H(H00X,H00Y,H), C00I(H00Z,HA,HB), C00L(H1,
 HD,HE), C00M(H2,HF,HG), C00N(H3,HH,HI), C00O(H4,HJ,HK), C00P(H5,HL,HM),
 C00Q(H6,HN,HO)
;
_shelx_res_checksum              44691
_shelx_hkl_checksum              25228
_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 1.805
_oxdiff_exptl_absorpt_empirical_full_min 0.492