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_7713595
_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         'C65 H51 N6 Y, C7 H8'
_chemical_formula_sum            'C72 H59 N6 Y'
_chemical_formula_weight         1097.16
_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     dual
_audit_creation_date             2022-03-30
_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                92.2250(10)
_cell_angle_beta                 91.3580(10)
_cell_angle_gamma                94.6340(10)
_cell_formula_units_Z            2
_cell_length_a                   11.9372(7)
_cell_length_b                   15.1671(8)
_cell_length_c                   16.1955(9)
_cell_measurement_reflns_used    9096
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      20.42
_cell_measurement_theta_min      2.20
_cell_volume                     2919.4(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker D8 Venture 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      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_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  0.0521
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34612
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.565
_diffrn_reflns_theta_min         1.259
_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    1.047
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4696
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0879 before and 0.0561 after correction.
The Ratio of minimum to maximum transmission is 0.6298.
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    1.248
_exptl_crystal_description       block
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.510
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     754
_refine_ls_number_reflns         13267
_refine_ls_number_restraints     393
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1045
_refine_ls_R_factor_gt           0.0547
_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^)+(0.0650P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1185
_refine_ls_wR_factor_ref         0.1357
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8248
_reflns_number_total             13267
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01714a2.cif
_cod_data_source_block           2b
_cod_database_code               7713595
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.818
_shelx_estimated_absorpt_t_min   0.802
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C66-C71 \\sim C66A-C71A
 with sigma of 0.02
 C71-C72 \\sim C71A-C72A
 with sigma of 0.02
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 C66-C72 \\sim C66A-C72A
 with sigma of 0.04
 C70-C72 \\sim C70A-C72A
 with sigma of 0.04
 C71-C70 \\sim C71A-C70A
 with sigma of 0.02
 C72-C71 \\sim C72A-C71A
 with sigma of 0.02
 C69-C68 \\sim C69A-C68A
 with sigma of 0.02
 C69-C70 \\sim C69A-C70A
 with sigma of 0.02
 C68-C67 \\sim C68A-C67A
 with sigma of 0.02
 C66-C68 \\sim C66A-C68A
 with sigma of 0.04
 C66-C70 \\sim C66A-C70A
 with sigma of 0.04
 C71-C69 \\sim C71A-C69A
 with sigma of 0.04
 C71-C67 \\sim C71A-C67A
 with sigma of 0.04
 C69-C67 \\sim C69A-C67A
 with sigma of 0.04
 C68-C70 \\sim C68A-C70A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C66 \\sim C71 \\sim C69 \\sim C68 \\sim C67 \\sim C70 \\sim C72 \\sim C72A
\\sim C70A \\sim C71A \\sim C66A \\sim C67A \\sim C68A \\sim C69A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C68) \\sim Ueq, Uanis(C67A) \\sim Ueq, Uanis(C69A) \\sim Ueq, Uanis(C70)
\\sim Ueq, Uanis(C71A) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C68A) \\sim Ueq,
Uanis(C67) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70A)
\\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C72A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C72A, C70A, C71A, C66A, C67A, C68A, C69A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C66, C71, C69, C68, C67, C70, C72
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C71A)=Sof(C70A)=Sof(H70A)=
 Sof(C69A)=Sof(H69A)=Sof(C68A)=Sof(H68A)=Sof(C67A)=Sof(H67A)=Sof(C66A)=
 Sof(H66A)=1-FVAR(1)
 Sof(C71)=Sof(C70)=Sof(H70)=Sof(C69)=Sof(H69)=Sof(C68)=Sof(H68)=Sof(C67)=
 Sof(H67)=Sof(C66)=Sof(H66)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(1)
6.a Riding coordinates:
 C72A(H72D,H72E,H72F)
6.b Ternary CH refined with riding coordinates:
 C19(H19), C20(H20)
6.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C3(H3), C2(H2), C1(H1), C11(H11), C38(H38), C17(H17), C31(H31),
 C48(H48), C7(H7), C29(H29), C37(H37), C53(H53), C52(H52), C16(H16), C35(H35),
 C13(H13), C15(H15), C58(H58), C32(H32), C25(H25), C10(H10), C57(H57), C14(H14),
  C26(H26), C8(H8), C42(H42), C61(H61), C49(H49), C55(H55), C65(H65), C34(H34),
 C28(H28), C51(H51), C56(H56), C33(H33), C27(H27), C46(H46), C50(H50), C63(H63),
  C9(H9), C62(H62), C64(H64), C45(H45), C43(H43), C44(H44), C70(H70), C69(H69),
 C68(H68), C67(H67), C66(H66), C70A(H70A), C69A(H69A), C68A(H68A), C67A(H67A),
 C66A(H66A)
6.d Fitted hexagon refined as free rotating group:
 C71(C70,C69,C68,C67,C66), C71A(C70A,C69A,C68A,C67A,C66A)
6.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              76853
_olex2_submission_special_instructions 'No special instructions were received'