Rare-earth metal complexes bearing electrophilic and nucleophilic carbon centres and their unique reactivity patterns towards pyridine derivatives.
Wu, Weikang; Rajeshkumar, Thayalan; Zhu, Shan; Chai, Fuxiang; Hong, Dongjing; Huang, Zeming; Yuan, Qingbing; Maron, Laurent; Wang, Shaowu; Chemical science 15 (2024) 20315–20327; doi:10.1039/d4sc04197f

data_1573130
_publ_section_title
;
 Rare-earth metal complexes bearing electrophilic and nucleophilic carbon
 centres and their unique reactivity patterns towards pyridine
 derivatives.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              20315
_journal_page_last               20327
_journal_paper_doi               10.1039/d4sc04197f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C60 H83 N6 Si Yb'
_chemical_formula_sum            'C60 H83 N6 Si Yb'
_chemical_formula_weight         1089.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-04-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-29 deposited with the CCDC.	2024-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                72.565(5)
_cell_angle_beta                 84.873(5)
_cell_angle_gamma                70.974(5)
_cell_formula_units_Z            2
_cell_length_a                   13.372(5)
_cell_length_b                   13.624(6)
_cell_length_c                   18.823(8)
_cell_measurement_reflns_used    9509
_cell_measurement_temperature    300
_cell_measurement_theta_max      22.29
_cell_measurement_theta_min      2.26
_cell_volume                     3093(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker SMART APEX II diffractometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      300
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0543
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30465
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.398
_diffrn_reflns_theta_min         1.134
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.570
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.3587
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1214 before and 0.0543 after correction.
The Ratio of minimum to maximum transmission is 0.4814.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_description       block
_exptl_crystal_F_000             1138
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         2.016
_refine_diff_density_min         -1.473
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1037
_refine_ls_number_reflns         11303
_refine_ls_number_restraints     1468
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1066
_refine_ls_R_factor_gt           0.0674
_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^)+(0.0727P)^2^+7.4951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1522
_refine_ls_wR_factor_ref         0.1698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7847
_reflns_number_total             11303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04197f3.cif
_cod_data_source_block           2b
_cod_depositor_comments
'Adding full bibliography for 1573095--1573138.cif.'
_cod_database_code               1573130
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.765
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil as less as possible was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C9, C9A}
3. Restrained distances
 Si1-C57 \\sim Si1-C58 \\sim Si1-C59 \\sim Si1-C60
 with sigma of 0.02
 C57-C58 \\sim C57-C59 \\sim C57-C60 \\sim C58-C59 \\sim C58-C60 \\sim C59-C60
 with sigma of 0.02
 Yb1-C57 \\sim Yb1-C57A \\sim Yb1-C57B
 with sigma of 0.02
 N1-C8A \\sim N1-C8
 with sigma of 0.02
 C3A-C2 \\sim C3-C2
 with sigma of 0.02
4. Restrained planarity
 C20, C18, C17, C21, C19, C22, N3, C26
 with sigma of 0.1
 C22A, C18A, C19A, C21A, C17A, C20A, C26A, C23A, N3
 with sigma of 0.1
 C5A, C3A, C8A, C6A, C4A, C7A, C2, N1
 with sigma of 0.1
 C5, C3, C8, C6, C4, C7, N1, C2
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Si1 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim Si1A \\sim C57A \\sim C58A
\\sim C59A \\sim C60A \\sim Si1B \\sim C57B \\sim C58B \\sim C59B \\sim C60B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N5 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim N5A \\sim
C38A \\sim C39A \\sim C40A \\sim C41A \\sim C42A \\sim C43A \\sim C37 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim
C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim
C28A \\sim N3 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C3A
\\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C2 \\sim N2 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim N2A \\sim C9A
\\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim N1
\\sim C51 \\sim C52 \\sim C53 \\sim C52A \\sim C53A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C9) = Uanis(C9A)
6. Same fragment restrains
{N1, N2A, C9A, C10A, C11A, C12A, C13A, C14A, C15A} sigma for 1-2: 0.02, 1-3:
0.04
as in
{N1, N2, C9, C10, C11, C12, C13, C14, C15}
{Si1A, C57A, C58A, C59A, C60A} sigma for 1-2: 0.02, 1-3: 0.04
{Si1B, C57B, C58B, C59B, C60B} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Si1, C57, C58, C59, C60}
{C3A, C4A, C5A, C6A, C7A, C8A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C3, C4, C5, C6, C7, C8}
{N3, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{N3, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28}
{C37, N5A, C38A, C39A, C40A, C41A, C42A, C43A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, N5, C38, C39, C40, C41, C42, C43}
{C51, C52A, C53A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C51, C52, C53}
7. Others
 1*[Sof(Si1)+Sof(C57)+Sof(H57A)+Sof(H57B)+Sof(C58)+Sof(H58A)+Sof(H58B)+
 Sof(H58C)+Sof(C59)+Sof(H59A)+Sof(H59B)+Sof(H59C)+Sof(C60)+Sof(H60A)+Sof(H60B)+
 Sof(H60C)]+1*[Sof(Si1A)+Sof(C57A)+Sof(H57C)+Sof(H57D)+Sof(C58A)+Sof(H58D)+
 Sof(H58E)+Sof(H58F)+Sof(C59A)+Sof(H59D)+Sof(H59E)+Sof(H59F)+Sof(C60A)+
 Sof(H60D)+Sof(H60E)+Sof(H60F)]+1*[Sof(Si1B)+Sof(C57B)+Sof(H57E)+Sof(H57F)+
 Sof(C58B)+Sof(H58G)+Sof(H58H)+Sof(H58I)+Sof(C59B)+Sof(H59G)+Sof(H59H)+
 Sof(H59I)+Sof(C60B)+Sof(H60G)+Sof(H60H)+Sof(H60I)]=1 with esd of 0
 Sof(Si1)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 FVAR(1)
 Sof(Si1A)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=Sof(H58D)=Sof(H58E)=
 Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60A)=Sof(H60D)=
 Sof(H60E)=Sof(H60F)=FVAR(2)
 Sof(Si1B)=Sof(C57B)=Sof(H57E)=Sof(H57F)=Sof(C58B)=Sof(H58G)=Sof(H58H)=
 Sof(H58I)=Sof(C59B)=Sof(H59G)=Sof(H59H)=Sof(H59I)=Sof(C60B)=Sof(H60G)=
 Sof(H60H)=Sof(H60I)=FVAR(3)
 Sof(N2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=
 Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13C)=
 Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(4)
 Sof(N2)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=
 Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(4)
 Sof(H37C)=Sof(H37D)=Sof(N5A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=
 Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=
 Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=1-FVAR(5)
 Sof(H37A)=Sof(H37B)=Sof(N5)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=FVAR(5)
 Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=
 Sof(H28F)=1-FVAR(6)
 Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(6)
 Sof(H51A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=1-FVAR(7)
 Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=FVAR(7)
 Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=
 Sof(H7A)=Sof(C8A)=1-FVAR(8)
 Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=
 Sof(C8)=FVAR(8)
8.a Riding coordinates:
 C58(H58A,H58B,H58C), C24A(H24D,H24E,H24F), C58B(H58G,H58H,H58I)
8.b Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C51(H51A), C51(H51), C54(H54), C23A(H23A), C26A(H26A)
8.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C37(H37A,H37B), C37(H37C,H37D), C38(H38A,H38B),
  C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,
 H43B), C57(H57A,H57B), C57A(H57C,H57D), C9A(H9AA,H9AB), C10A(H10C,H10D),
 C11A(H11C,H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,
 H15D), C38A(H38C,H38D), C39A(H39C,H39D), C40A(H40C,H40D), C41A(H41C,H41D),
 C42A(H42C,H42D), C43A(H43C,H43D), C57B(H57E,H57F)
8.d Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C16(H16), C32(H32), C33(H33), C34(H34),
 C35(H35), C44(H44), C47(H47), C48(H48), C49(H49), C4(H4), C5(H5), C6(H6),
 C7(H7), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C19A(H19A), C20A(H20A),
 C21A(H21A)
8.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C58A(H58D,H58E,H58F),
 C59A(H59D,H59E,H59F), C60A(H60D,H60E,H60F), C25A(H25D,H25E,H25F), C27A(H27D,
 H27E,H27F), C28A(H28D,H28E,H28F), C52A(H52D,H52E,H52F), C53A(H53D,H53E,H53F),
 C59B(H59G,H59H,H59I), C60B(H60G,H60H,H60I)
;
_shelx_res_checksum              27048
_shelx_hkl_checksum              36760
_olex2_submission_special_instructions 'No special instructions were received'