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_7713593
_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         'C51 H58 Lu N3 O2 Si'
_chemical_formula_sum            'C51 H58 Lu N3 O2 Si'
_chemical_formula_weight         948.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-09
_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                 120.84(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.50(6)
_cell_length_b                   12.35(3)
_cell_length_c                   17.13(4)
_cell_measurement_reflns_used    9924
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      24.712
_cell_measurement_theta_min      2.560
_cell_volume                     4995(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART APEX II diffractrometer'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298.15
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28265
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.571
_diffrn_reflns_theta_min         1.725
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.039
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3377
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1247 before and 0.0543 after correction.
The Ratio of minimum to maximum transmission is 0.4529.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       block
_exptl_crystal_F_000             1944
_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          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.337
_refine_diff_density_min         -2.252
_refine_diff_density_rms         0.197
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     490
_refine_ls_number_reflns         5690
_refine_ls_number_restraints     1883
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0793
_refine_ls_R_factor_gt           0.0685
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1127P)^2^+36.7701P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2029
_refine_ls_wR_factor_ref         0.2095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4843
_reflns_number_total             5690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01714a2.cif
_cod_data_source_block           1a'
_cod_original_cell_volume        4993(20)
_cod_database_code               7713593
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.792
_exptl_crystal_mounting_method
'The title complex was mounted in a sealed capillary.'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-C51 = O2-C48 = O1-C47 = O1-C44
 1.43 with sigma of 0.01
 C45-C44 = C46-C45 = C47-C46 = C49-C48 = C50-C49 = C51-C50
 1.54 with sigma of 0.01
 C48-C51 = C47-C44
 2.336 with sigma of 0.02
 C48-C50 = C51-C49 = C47-C45 = C44-C46
 2.515 with sigma of 0.02
 Si1-C41 \\sim Si1-C40 \\sim Si1-C42 \\sim Si1-C43
 with sigma of 0.02
 C41-C40 \\sim C42-C40 \\sim C43-C40 \\sim C43-C42 \\sim C42-C41 \\sim C43-C41
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C39 \\sim C38 \\sim C37 \\sim C36 \\sim C5
\\sim C6 \\sim C11 \\sim C10 \\sim C9 \\sim C8 \\sim C7 \\sim C12 \\sim C13
\\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C20 \\sim C19 \\sim C18 \\sim C21
\\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29
\\sim C30 \\sim C35 \\sim C34 \\sim C33 \\sim C32 \\sim C31 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3.8A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Fixed Sof: Lu1(0.5) Si1(0.5) O1(0.5) O2(0.5) N1(0.5) C1(0.5) H1(0.5) C2(0.5)
 H2(0.5) C3(0.5) H3(0.5) C4(0.5) N2(0.5) C39(0.5) H39(0.5) C38(0.5) H38(0.5)
 C37(0.5) H37(0.5) C36(0.5) C5(0.5) C6(0.5) C11(0.5) H11(0.5) C10(0.5) H10(0.5)
 C9(0.5) H9(0.5) C8(0.5) H8(0.5) C7(0.5) H7(0.5) C12(0.5) C13(0.5) H13(0.5)
 C14(0.5) H14(0.5) C15(0.5) H15(0.5) C16(0.5) H16(0.5) C17(0.5) H17(0.5)
 C20(0.5) H20(0.5) C19(0.5) H19(0.5) C18(0.5) N3(0.5) C21(0.5) C22(0.5)
 H22A(0.5) H22B(0.5) H22C(0.5) C23(0.5) C24(0.5) C25(0.5) H25(0.5) C26(0.5)
 H26(0.5) C27(0.5) H27(0.5) C28(0.5) H28(0.5) C29(0.5) H29(0.5) C30(0.5)
 C35(0.5) H35(0.5) C34(0.5) H34(0.5) C33(0.5) H33(0.5) C32(0.5) H32(0.5)
 C31(0.5) H31(0.5) C40(0.5) H40A(0.5) H40B(0.5) C41(0.5) H41A(0.5) H41B(0.5)
 H41C(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C43(0.5) H43A(0.5) H43B(0.5)
 H43C(0.5) C44(0.5) H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5) C46(0.5)
 H46A(0.5) H46B(0.5) C47(0.5) H47A(0.5) H47B(0.5) C48(0.5) H48A(0.5) H48B(0.5)
 C49(0.5) H49A(0.5) H49B(0.5) C50(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5)
 H51B(0.5)
6.a Riding coordinates:
 C43(H43A,H43B,H43C)
6.b Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,
 H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C39(H39), C38(H38), C37(H37), C11(H11), C10(H10),
 C9(H9), C8(H8), C7(H7), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C20(H20), C19(H19), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C35(H35),
  C34(H34), C33(H33), C32(H32), C31(H31)
6.d Fitted hexagon refined as free rotating group:
 C6(C11,C10,C9,C8,C7), C12(C13,C14,C15,C16,C17), C30(C35,C34,C33,C32,C31)
6.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C)
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_shelx_res_checksum              97271
_olex2_submission_special_instructions 'No special instructions were received'