Flow Rhodaelectro-Catalyzed Alkyne Annulations by Versatile C-H Activation: Mechanistic Support for Rhodium(III/IV).
Kong, Wei-Jun; Finger, Lars H.; Messinis, Antonis M.; Kuniyil, Rositha; Oliveira, João C A; Ackermann, Lutz; Journal of the American Chemical Society 141 (2019) 17198–17206; doi:10.1021/jacs.9b07763

data_4127877
_publ_section_title
;
 Flow Rhodaelectro-Catalyzed Alkyne Annulations by Versatile C-H
 Activation: Mechanistic Support for Rhodium(III/IV).
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17198
_journal_page_last               17206
_journal_paper_doi               10.1021/jacs.9b07763
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C27 H39 O3 Rh, C2 H3 O2, 1[C5H12]'
_chemical_formula_sum            'C34 H54 N O4 Rh'
_chemical_formula_weight         643.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                93.264(2)
_cell_angle_beta                 112.887(2)
_cell_angle_gamma                110.651(2)
_cell_formula_units_Z            4
_cell_length_a                   13.8448(12)
_cell_length_b                   16.4625(14)
_cell_length_c                   17.3541(12)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.517
_cell_measurement_theta_min      2.426
_cell_volume                     3322.3(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            257861
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.581
_diffrn_reflns_theta_min         2.424
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.550
_exptl_absorpt_correction_T_max  0.4621
_exptl_absorpt_correction_T_min  0.4282
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1388 before and 0.0544 after correction. The Ratio of minimum to maximum transmission is 0.9266. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       needle
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.332
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.553
_refine_diff_density_min         -1.338
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     813
_refine_ls_number_reflns         20355
_refine_ls_number_restraints     716
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0420P)^2^+4.3973P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0973
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17867
_reflns_number_total             20355
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07763_si_006.cif
_cod_data_source_block           0713_cg_0m
_cod_database_code               4127877
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.839
_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
 N1-H1 = O3-H3 = O7-H7 = N2-H2
 0.9 with sigma of 0.02
 C69-C68 \\sim C68-C67 \\sim C67-C66 \\sim C66-C65
 with sigma of 0.02
 C69-C67 \\sim C67-C65 \\sim C68-C66
 with sigma of 0.04
 C74-C73 \\sim C73-C72 \\sim C72-C71 \\sim C71-C70
 with sigma of 0.02
 C74-C72 \\sim C72-C70 \\sim C73-C71
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C39 \\sim C45: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C65, C66, C67, C68, C69
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Rh1, O2, O3, N1, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14,
 C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Rh2, O6, O7, N2, C30, C31, C32, C33, C34, C35, C36, C37, C44, C45, C46, C47,
 C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C44, C45, C46, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C39, C41, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C70, C71, C72, C73, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=1-FVAR(1)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=0.68*(1-
 FVAR(2))
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=0.32*(1-
 FVAR(2))
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C38(H38A,H38B), C39(H39A,H39B),
 C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C71(H71A,H71B), C72(H72A,
 H72B), C73(H73A,H73B)
6.b Me refined with riding coordinates:
 C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C47(H47A,H47B,H47C), C70(H70A,H70B,
 H70C), C74(H74A,H74B,H74C)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C48(H48), C49(H49), C50(H50), C51(H51)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C17(H17A,H17B,H17C),
 C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C52(H52A,
 H52B,H52C), C55(H55A,H55B,H55C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C29(H29A,H29B,H29C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              2093
_shelx_hkl_checksum              84335
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in NVH oil'
_olex2_submission_special_instructions 'No special instructions were received'