Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes
Guo, Dianjun; Rajeshkumar, Thayalan; Zhu, Shan; Yuan, Qingbing; Hong, Dongjing; Zhou, Shuangliu; Zhu, Xiancui; Maron, Laurent; Wang, Shaowu; Dalton Transactions  (2023) –; doi:10.1039/D3DT01714A

data_7713607
_publ_section_title
;
 Aryl C--H bond functionalization with diphenyldiazomethane induced by
 rare-earth metal alkyl complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01714A
_journal_year                    2023
_chemical_formula_moiety         'C57 H55 N4 Si Y'
_chemical_formula_sum            'C57 H55 N4 Si Y'
_chemical_formula_weight         913.05
_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     dual
_audit_creation_date             2022-03-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-13 deposited with the CCDC.	2023-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.46(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.37(2)
_cell_length_b                   10.679(18)
_cell_length_c                   36.16(6)
_cell_measurement_reflns_used    7975
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      19.413
_cell_measurement_theta_min      2.221
_cell_volume                     5457(15)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_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  0.1223
_diffrn_reflns_av_unetI/netI     0.1133
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            62836
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.589
_diffrn_reflns_theta_min         1.145
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.127
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4054
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1000 before and 0.0597 after correction. The Ratio of minimum to maximum transmission is 0.5437. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.111
_exptl_crystal_description       block
_exptl_crystal_F_000             1912
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     654
_refine_ls_number_reflns         12492
_refine_ls_number_restraints     422
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1574
_refine_ls_R_factor_gt           0.0691
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0791P)^2^+0.1712P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1497
_refine_ls_wR_factor_ref         0.1791
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5964
_reflns_number_total             12492
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01714a2.cif
_cod_data_source_block           6
_cod_original_cell_volume        5458(16)
_cod_database_code               7713607
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.806
_shelx_estimated_absorpt_t_min   0.790
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C56-C55 \\sim C56-C54 \\sim C55-C54
 with sigma of 0.02
 C56A-C55A \\sim C55A-C54A \\sim C56A-C54A
 with sigma of 0.02
 Si1A-C53 \\sim Si1-C53
 with sigma of 0.02
 Si1A-C56A \\sim Si1A-C54A \\sim Si1A-C55A
 with sigma of 0.02
 Si1-C56 \\sim Si1-C54 \\sim Si1-C55
 with sigma of 0.02
 N4-C46 \\sim N4-C46A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si1 \\sim C56 \\sim C55 \\sim C54 \\sim C55A \\sim C56A \\sim C54A \\sim Si1A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C46 \\sim C51 \\sim C50 \\sim C49 \\sim C48 \\sim C47 \\sim C52 \\sim C52A
\\sim C51A \\sim C50A \\sim C49A \\sim C48A \\sim C47A \\sim C46A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C56, C54, Si1, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C56A, C55A, Si1A, C54A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C52, C51, C50, C49, C48, C47, C46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C52A, C51A, C50A, C49A, C47A, C48A, C46A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H53C)=Sof(H53D)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C56A)=
 Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=
 Sof(Si1A)=1-FVAR(1)
 Sof(Si1)=Sof(H53A)=Sof(H53B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C55)=
 Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(1)
 Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C46A)=Sof(C51A)=Sof(C50A)=
 Sof(H50A)=Sof(C49A)=Sof(H49A)=Sof(C48A)=Sof(H48A)=Sof(C47A)=Sof(H47A)=1-FVAR(2)
 Sof(C46)=Sof(C51)=Sof(C50)=Sof(H50)=Sof(C49)=Sof(H49)=Sof(C48)=Sof(H48)=
 Sof(C47)=Sof(H47)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C20(H20), C19(H19), C40(H40)
6.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C53(H53C,H53D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C1(H1), C11(H11), C31(H31), C34(H34), C17(H17), C35(H35),
 C50(H50), C49(H49), C48(H48), C47(H47), C13(H13), C25(H25), C32(H32), C33(H33),
  C29(H29), C39(H39), C42(H42), C37(H37), C10(H10), C7(H7), C26(H26), C27(H27),
 C16(H16), C28(H28), C38(H38), C15(H15), C9(H9), C45(H45), C8(H8), C43(H43),
 C44(H44), C01I(H01I), C14(H14), C50A(H50A), C49A(H49A), C48A(H48A), C47A(H47A)
6.d Fitted hexagon refined as free rotating group:
 C46(C51,C50,C49,C48,C47), C46A(C51A,C50A,C49A,C48A,C47A)
6.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C52(H52A,H52B,H52C), C56(H56A,H56B,H56C), C55(H55A,H55B,
 H55C), C54(H54A,H54B,H54C), C55A(H55D,H55E,H55F), C56A(H56D,H56E,H56F),
 C54A(H54D,H54E,H54F), C52A(H52D,H52E,H52F)
;
_shelx_res_checksum              46709
_shelx_fab_checksum              1055
_olex2_submission_special_instructions 'No special instructions were received'