The Role of Neutral Donor Ligands in the Isoselective Ring-Opening Polymerization of rac-β-Butyrolactone
Dong, Xiang; Robinson, Jerome; Chemical Science  (2020) –; doi:10.1039/D0SC03507F

data_1558610
_publ_section_title
;
 The Role of Neutral Donor Ligands in the Isoselective Ring-Opening
 Polymerization of rac-\b-Butyrolactone
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03507F
_journal_year                    2020
_chemical_formula_moiety         'C77 H95 La N2 O4 P2 Si2, 2[C7H8]'
_chemical_formula_sum            'C91 H111 La N2 O4 P2 Si2'
_chemical_formula_weight         1553.84
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-26
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-01-26 deposited with the CCDC.	2020-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.563(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.355(2)
_cell_length_b                   15.378(2)
_cell_length_c                   35.734(5)
_cell_measurement_reflns_used    9162
_cell_measurement_temperature    173.21
_cell_measurement_theta_max      27.57
_cell_measurement_theta_min      2.61
_cell_volume                     8411.1(19)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.21
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8-Quest, Photon 100 CMOS Detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1040
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            152196
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.600
_diffrn_reflns_theta_min         1.931
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.624
_exptl_absorpt_correction_T_max  0.6207
_exptl_absorpt_correction_T_min  0.5498
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1371 before and 0.1251 after correction.
The Ratio of minimum to maximum transmission is 0.8858.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       block
_exptl_crystal_F_000             3272
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.484
_refine_diff_density_min         -0.893
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     886
_refine_ls_number_reflns         19424
_refine_ls_number_restraints     175
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0753P)^2^+5.3901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1315
_refine_ls_wR_factor_ref         0.1399
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15883
_reflns_number_total             19424
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03507f2.cif
_cod_data_source_block           jrr20190225_1-La(TPPO)2
_cod_original_cell_volume        8411(2)
_cod_database_code               1558610
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.918
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All Si(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C9-C10 \\sim C9-C11 \\sim C9-C10A \\sim C9-C11A
 with sigma of 0.02
 C9-C12 \\sim C9-C12A
 with sigma of 0.02
 C8-C10 \\sim C8-C11 \\sim C8-C10A \\sim C8-C11A
 with sigma of 0.04
 C8-C12 \\sim C11-C12 \\sim C8-C12A \\sim C11A-C12A
 with sigma of 0.04
 C10-C11 \\sim C10-C12 \\sim C10A-C11A \\sim C10A-C12A
 with sigma of 0.04
 C27-C28 \\sim C27-C29 \\sim C27-C28A \\sim C27-C29A
 with sigma of 0.02
 C27-C30 \\sim C27-C30A
 with sigma of 0.02
 C26-C28 \\sim C26-C29 \\sim C26-C28A \\sim C26-C29A
 with sigma of 0.04
 C26-C30 \\sim C27-C28 \\sim C26-C30A \\sim C28A-C29A
 with sigma of 0.04
 C28-C30 \\sim C29-C30 \\sim C28A-C30A \\sim C29A-C30A
 with sigma of 0.04
 Si2-C41 \\sim Si2-C41A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si2 \\sim C41 \\sim C41A: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
4. Rigid body (RIGU) restrains
 Si2, C41, C41A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8, C9, C10A, C11A, C12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H2A)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=1-FVAR(1)
 Sof(H2B)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=FVAR(1)
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(2)
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(3)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 Si2(H2A), Si2(H2B)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C23(H23A,H23B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25),
 C31(H31), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C49(H49), C50(H50),
  C51(H51), C52(H52), C53(H53), C55(H55), C56(H56), C57(H57), C58(H58),
 C59(H59), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68),
  C69(H69), C70(H70), C71(H71), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77)
6.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C12A(H12D,H12E,H12F), C28A(H28D,
 H28E,H28F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F), C41(H41A,H41B,H41C),
 C41A(H41D,H41E,H41F)
;
_shelx_res_checksum              22916
_shelx_fab_checksum              30774
_platon_squeeze_special_details
;
'The unit cell contains 8 toluene molecules which have been treated
as a diffuse contribution to the overall scattering without specific atom
positions by SQUEEZE/PLATON.'
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'