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_7713596
_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         'C69 H59 Lu N6 O'
_chemical_formula_sum            'C69 H58 Lu N6 O'
_chemical_formula_weight         1162.18
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
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2022-08-13 deposited with the CCDC.	2023-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                77.87(4)
_cell_angle_beta                 86.86(9)
_cell_angle_gamma                64.85(4)
_cell_formula_units_Z            2
_cell_length_a                   14.08(5)
_cell_length_b                   16.13(6)
_cell_length_c                   17.56(6)
_cell_measurement_reflns_used    4496
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      19.20
_cell_measurement_theta_min      2.37
_cell_volume                     3527(2)
_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 0.996
_diffrn_measured_fraction_theta_max 0.969
_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  0.1498
_diffrn_reflns_av_unetI/netI     0.2362
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            39132
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.584
_diffrn_reflns_theta_min         1.425
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.439
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5256
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0968 before and 0.0743 after correction.
The Ratio of minimum to maximum transmission is 0.7049.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dull light black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.094
_exptl_crystal_description       block
_exptl_crystal_F_000             1186
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.798
_refine_diff_density_min         -1.732
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.913
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     729
_refine_ls_number_reflns         15852
_refine_ls_number_restraints     1248
_refine_ls_restrained_S_all      0.892
_refine_ls_R_factor_all          0.1591
_refine_ls_R_factor_gt           0.0733
_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^)+(0.0630P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1487
_refine_ls_wR_factor_ref         0.1773
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7517
_reflns_number_total             15852
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01714a2.cif
_cod_data_source_block           2a'
_cod_original_cell_volume        3528(22)
_cod_database_code               7713596
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.762
_shelx_estimated_absorpt_t_min   0.743
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Lu1-O1 \\sim Lu1-O1A
 with sigma of 0.02
 O1-C01A \\sim O1A-C01B
 with sigma of 0.02
 O1-C01D \\sim O1A-C01E
 with sigma of 0.02
 C00M-C01D \\sim C00N-C01E
 with sigma of 0.02
 C00M-C01P \\sim C00N-C01Q
 with sigma of 0.02
 C01A-C01P \\sim C01B-C01Q
 with sigma of 0.02
 Lu1-C01A \\sim Lu1-C01B
 with sigma of 0.04
 Lu1-C01D \\sim Lu1-C01E
 with sigma of 0.04
 O1-C00M \\sim O1A-C00N
 with sigma of 0.04
 O1-C01P \\sim O1A-C01Q
 with sigma of 0.04
 C00M-C01A \\sim C00N-C01B
 with sigma of 0.04
 C01A-C01D \\sim C01B-C01E
 with sigma of 0.04
 C01D-C01P \\sim C01E-C01Q
 with sigma of 0.04
 Lu1-O1A \\sim Lu1-O1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C60 \\sim C61 \\sim C65 \\sim C64 \\sim C62 \\sim C63 \\sim C36: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C9 \\sim C8 \\sim C7 \\sim C6 \\sim C11 \\sim C10 \\sim N2: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim C39 \\sim C38 \\sim C37 \\sim C36: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O1 \\sim C00M \\sim C01A \\sim C01D \\sim C01P \\sim C00N \\sim C01Q \\sim C01B
\\sim C01E \\sim O1A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
Uanis(C23) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1) \\sim Ueq, Uanis(C00M) \\sim Ueq, Uanis(C01A) \\sim Ueq, Uanis(C01D)
\\sim Ueq, Uanis(C01P) \\sim Ueq, Uanis(C00N) \\sim Ueq, Uanis(C01Q) \\sim Ueq,
Uanis(C01B) \\sim Ueq, Uanis(C01E) \\sim Ueq, Uanis(O1A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C00M) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C00N)=Sof(H00C)=Sof(H00D)=Sof(C01Q)=Sof(H01G)=Sof(H01H)=Sof(C01B)=
 Sof(H01I)=Sof(H01J)=Sof(C01E)=Sof(H01K)=Sof(H01L)=Sof(O1A)=1-FVAR(1)
 Sof(O1)=Sof(C00M)=Sof(H00A)=Sof(H00B)=Sof(C01A)=Sof(H01A)=Sof(H01B)=Sof(C01D)=
 Sof(H01C)=Sof(H01D)=Sof(C01P)=Sof(H01E)=Sof(H01F)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C20(H20)
6.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B), C01A(H01A,H01B), C01D(H01C,H01D), C01P(H01E,H01F), C00N(H00C,
 H00D), C01Q(H01G,H01H), C01B(H01I,H01J), C01E(H01K,H01L)
6.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C37(H37), C38(H38), C52(H52), C51(H51), C50(H50), C49(H49), C48(H48),
 C17(H17), C35(H35), C2(H2), C42(H42), C34(H34), C3(H3), C25(H25), C31(H31),
 C39(H39), C55(H55), C1(H1), C61(H61), C58(H58), C7(H7), C29(H29), C65(H65),
 C13(H13), C28(H28), C27(H27), C11(H11), C15(H15), C46(H46), C33(H33), C57(H57),
  C32(H32), C45(H45), C56(H56), C26(H26), C8(H8), C9(H9), C44(H44), C64(H64),
 C43(H43), C16(H16), C14(H14), C10(H10), C62(H62), C63(H63)
6.d Fitted hexagon refined as free rotating group:
 C47(C52,C51,C50,C49,C48)
6.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_shelx_res_checksum              37825
_shelx_fab_checksum              43983
_olex2_submission_special_instructions 'No special instructions were received'