Site-Selective Carbene-Induced C–H Functionalization Catalyzed by Dirhodium Tetrakis(triarylcyclopropanecarboxylate) Complexes
Liao, Kuangbiao; Liu, Wenbin; Niemeyer, Zachary L.; Ren, Zhi; Bacsa, John; Musaev, Djamaladdin G.; Sigman, Mathew S.; Davies, Huw M. L.; ACS Catalysis 8 (2017) 678–; doi:10.1021/acscatal.7b03421

data_4514319
_publ_section_title
;
 Site-Selective Carbene-Induced C--H Functionalization Catalyzed by
 Dirhodium Tetrakis(triarylcyclopropanecarboxylate) Complexes
;
_journal_issue                   1
_journal_name_full               'ACS Catalysis'
_journal_page_first              678
_journal_paper_doi               10.1021/acscatal.7b03421
_journal_volume                  8
_journal_year                    2017
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C120 H104 O10 Rh2, C4 H10 O'
_chemical_formula_sum            'C124 H114 O11 Rh2'
_chemical_formula_weight         1985.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-08-16
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.389(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.764(3)
_cell_length_b                   17.436(4)
_cell_length_c                   26.079(7)
_cell_measurement_reflns_used    9996
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.378
_cell_measurement_theta_min      2.254
_cell_volume                     5348(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device_type  'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.1311
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19801
_diffrn_reflns_point_group_measured_fraction_full 0.832
_diffrn_reflns_point_group_measured_fraction_max 0.832
_diffrn_reflns_theta_full        24.713
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         1.562
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           35
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.368
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6011
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0922 before and 0.0599 after correction. The Ratio of minimum to maximum transmission is 0.8066. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'greenish blue'
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       plate
_exptl_crystal_F_000             2072
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.476
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.398
_refine_diff_density_min         -1.430
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Flack x determined using 3127 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1240
_refine_ls_number_reflns         15161
_refine_ls_number_restraints     1416
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.1395
_refine_ls_R_factor_gt           0.0987
_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^)+(0.0002P)^2^+61.2351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1964
_refine_ls_wR_factor_ref         0.2181
_reflns_Friedel_coverage         0.661
_reflns_Friedel_fraction_full    0.687
_reflns_Friedel_fraction_max     0.687
_reflns_number_gt                10889
_reflns_number_total             15161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b03421_si_003.cif
_cod_data_source_block           s-bpcp_0m
_cod_depositor_comments
'Adding full bibliography for 4514318--4514319.cif.'
_cod_original_cell_volume        5347(2)
_cod_database_code               4514319
_shelx_shelxl_version_number     2014/7
_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
 C118-C117
 1.52 with sigma of 0.01
 C2-C1 \\sim C4-C3 \\sim C120-C119 \\sim C118-C117
 with sigma of 0.004
 C38-C37 \\sim C42-C37
 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(C117) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(O9) \\sim Ueq, Uanis(O8) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.008
Uanis(C89) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C33) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O10) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C5) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O8) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 C10, Rh1, O5, O7, O3, O9, O10, Rh2, C33, C61, C5, C89, C117, C119, O8, O2, O4,
  O6, O1, C34, C62, C6, C90, C118, C120, C1, C3, C35, C36, C49, C63, C64, C77,
 C7, C8, C21, C91, C92, C105, C2, C4, C37, C43, C50, C54, C65, C71, C78, C82,
 C9, C15, C22, C26, C93, C99, C106, C110, C38, C42, C44, C48, C51, C53, C66,
 C70, C72, C76, C79, C81, C14, C16, C20, C23, C25, C94, C98, C100, C104, C107,
 C109, C39, C41, C45, C47, C52, C67, C69, C73, C75, C80, C11, C13, C17, C19,
 C24, C95, C97, C101, C103, C108, C40, C46, C55, C68, C74, C83, C12, C18, C27,
 C96, C102, C111, C56, C60, C84, C88, C28, C32, C112, C116, C57, C59, C85, C87,
 C29, C31, C113, C115, C58, C86, C30, C114
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32} sigma for 1-2:
0.002, 1-3: 0.004
as
{C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60}
{C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32} sigma for 1-2:
0.002, 1-3: 0.004
as
{C77, C78, C79, C80, C81, C82, C83, C84, C85, C86, C87, C88}
{C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32} sigma for 1-2:
0.002, 1-3: 0.004
as
{C105, C106, C107, C108, C109, C110, C111, C112, C113, C114, C115, C116}
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C8(H8A,H8B), C36(H36A,H36B), C64(H64A,H64B),
 C92(H92A,H92B), C117(H11A,H11B), C119(H11F,H11G), C1A(H1AA,H1AB), C1C(H1CA,
 H1CB)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C32(H32), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C50(H50),
  C51(H51), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
 C60(H60), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C72(H72), C73(H73),
  C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C81(H81), C82(H82),
 C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C94(H94), C95(H95), C96(H96),
  C97(H97), C98(H98), C100(H100), C101(H101), C102(H102), C103(H103),
 C104(H104), C106(H106), C107(H107), C109(H109), C110(H110), C112(H112),
 C113(H113), C114(H114), C115(H115), C116(H116)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C118(H11C,H11D,H11E), C120(H12A,H12B,H12C),
 C1B(H1BA,H1BB,H1BC), C9BA(H9BA,H9BB,H9BC)
;
_shelx_res_checksum              85811
_shelx_hkl_checksum              11410
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id S-BPCP
_olex2_submission_special_instructions 'No special instructions were received'