Mechanism Studies of Ir-Catalyzed Asymmetric Hydrogenation of Unsaturated Carboxylic Acids.
Li, Mao-Lin; Yang, Shuang; Su, Xun-Cheng; Wu, Hui-Ling; Yang, Liang-Liang; Zhu, Shou-Fei; Zhou, Qi-Lin; Journal of the American Chemical Society 139 (2017) 541–547; doi:10.1021/jacs.6b11655

data_4125638
_publ_section_title
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 Mechanism Studies of Ir-Catalyzed Asymmetric Hydrogenation of Unsaturated
 Carboxylic Acids.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              541
_journal_page_last               547
_journal_paper_doi               10.1021/jacs.6b11655
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C106 H133 Ir2 N2 O4 P2, C F3 O3 S, 2(C6 H6)'
_chemical_formula_sum            'C119 H145 F3 Ir2 N2 O7 P2 S'
_chemical_formula_weight         2250.77
_chemical_name_systematic
;
 ? 
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_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 109.25(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   13.965(3)
_cell_length_b                   28.537(6)
_cell_length_c                   14.700(3)
_cell_measurement_reflns_used    14855
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.9143
_cell_measurement_theta_min      1.4674
_cell_volume                     5531(2)
_computing_cell_refinement       CrystalClear
_computing_data_collection       CrystalClear
_computing_data_reduction        CrystalClear'
_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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 7.31
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  multi-scan
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0694
_diffrn_reflns_av_unetI/netI     0.1215
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            54950
_diffrn_reflns_theta_full        27.91
_diffrn_reflns_theta_max         27.91
_diffrn_reflns_theta_min         1.43
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    2.511
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6336
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   CrystalClear
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             2312
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.805
_refine_diff_density_min         -1.277
_refine_diff_density_rms         0.175
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.020(6)
_refine_ls_extinction_coef       0.00311(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1306
_refine_ls_number_reflns         23798
_refine_ls_number_restraints     380
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.0717
_refine_ls_R_factor_gt           0.0537
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0359P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1074
_refine_ls_wR_factor_ref         0.1201
_reflns_number_gt                19471
_reflns_number_total             23798
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja6b11655_si_002.cif
_cod_data_source_block           shelxl
_cod_original_cell_volume        5530.5(19)
_cod_database_code               4125638
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H78A,H78B,H78C} of C78, {H33A,H33B,H33C} of C33, {H34A,
  H34B,H34C} of C34, All C(H,H) groups
 At 1.5 times of:
  All Ir(H) groups, {H81D,H81E,H81F} of C81A, {H82D,H82E,H82F} of C82A, {H80D,
  H80E,H80F} of C80A, {H80A,H80B,H80C} of C80B, {H81A,H81B,H81C} of C81B, {H82A,
  H82B,H82C} of C82B, {H99A,H99B,H99C} of C99, {H94A,H94B,H94C} of C94, {H92A,
  H92B,H92C} of C92, {H91A,H91B,H91C} of C91, {H90A,H90B,H90C} of C90, {H77A,
  H77B,H77C} of C77, {H76A,H76B,H76C} of C76, {H96D,H96E,H96F} of C96', {H95D,
  H95E,H95F} of C95', {H94D,H94E,H94F} of C94', {H96A,H96B,H96C} of C96, {H95A,
  H95B,H95C} of C95, {H29A,H29B,H29C} of C29, {H30A,H30B,H30C} of C30, {H32A,
  H32B,H32C} of C32, {H42A,H42B,H42C} of C42, {H43A,H43B,H43C} of C43, {H44A,
  H44B,H44C} of C44, {H46A,H46B,H46C} of C46, {H47A,H47B,H47C} of C47, {H48A,
  H48B,H48C} of C48, {H28A,H28B,H28C} of C28, All Ir(H,H,H) groups
2. Restrained distances
 C93-C94 = C93-C95 = C93-C96 = C93-C94' = C93-C95' = C93-C96'
 1.54 with sigma of 0.01
 Ir1-H \\sim Ir2-HA
 with sigma of 0.01
 C80A-C79 \\sim C79-C80B
 with sigma of 0.02
 C82A-C79 \\sim C79-C82B
 with sigma of 0.02
 C81A-C79 \\sim C79-C81B
 with sigma of 0.02
 C81A-C79 \\sim C79-C80A
 with sigma of 0.02
 C80B-C79 \\sim C79-C82A
 with sigma of 0.02
 C82B-C79 \\sim C79-C81B
 with sigma of 0.02
 C81A-C80A \\sim C80A-C82A
 with sigma of 0.02
 C80A-C82A \\sim C82A-C81A
 with sigma of 0.02
 C82A-C81A \\sim C81A-C80A
 with sigma of 0.02
 Ir1-HB \\sim Ir2-HB \\sim Ir1-HC \\sim Ir2-HC
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C80A \\sim C80B \\sim C82A \\sim C82B \\sim C79 \\sim C81A \\sim C81B: within
3.8A with sigma of 0.005 and sigma for terminal atoms of 0.005
C90 \\sim C89 \\sim C91 \\sim C92: within 3.8A with sigma of 0.005 and sigma
for terminal atoms of 0.005
Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C116) \\sim Ueq,
Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C119) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C123) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C82B) \\sim Ueq, Uanis(C81B) \\sim Ueq, Uanis(C80B) \\sim Ueq,
Uanis(C82A) \\sim Ueq, Uanis(C81A) \\sim Ueq, Uanis(C80A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.005
Uanis(C49) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C94) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C94')
\\sim Ueq, Uanis(C95') \\sim Ueq, Uanis(C96') \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C80A) = Uanis(C80B)
Uanis(C82A) = Uanis(C82B)
Uanis(C81B) = Uanis(C81A)
Uanis(C96) = Uanis(C96')
4. Others
 Sof(C94')=Sof(H94D)=Sof(H94E)=Sof(H94F)=Sof(C95')=Sof(H95D)=Sof(H95E)=
 Sof(H95F)=Sof(C96')=Sof(H96D)=Sof(H96E)=Sof(H96F)=1-FVAR(1)
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=FVAR(1)
 Sof(C82B)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C81B)=Sof(H81A)=Sof(H81B)=
 Sof(H81C)=Sof(C80B)=Sof(H80A)=Sof(H80B)=Sof(H80C)=1-FVAR(2)
 Sof(C80A)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C82A)=Sof(H82D)=Sof(H82E)=
 Sof(H82F)=Sof(C81A)=Sof(H81D)=Sof(H81E)=Sof(H81F)=FVAR(2)
 Fixed Sof: C114(0.5) H114(0.5) C115(0.5) H115(0.5) C116(0.5) H116(0.5)
 C117(0.5) H117(0.5) C118(0.5) H118(0.5) C119(0.5) H119(0.5) C120(0.5)
 H120(0.5) C121(0.5) H121(0.5) C122(0.5) H122(0.5) C123(0.5) H123(0.5)
 C124(0.5) H124(0.5) C125(0.5) H125(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C9(H9A,H9B), C10(H10A,H10B), C13(H13A,H13B),
 C14(H14A,H14B), C49(H49A,H49B), C50(H50A,H50B), C57(H57A,H57B), C58(H58A,H58B),
  C61(H61A,H61B), C62(H62A,H62B)
5.b Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,
 H78C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C94(H94A,
 H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C94'(H94D,H94E,H94F),
 C95'(H95D,H95E,H95F), C96'(H96D,H96E,H96F), C99(H99A,H99B,H99C)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C22(H22), C24(H24),
 C26(H26), C36(H36), C38(H38), C40(H40), C53(H53), C54(H54), C55(H55), C64(H64),
  C65(H65), C66(H66), C70(H70), C72(H72), C74(H74), C84(H84), C86(H86),
 C88(H88), C100(H100), C102(H102), C103(H103), C104(H104), C105(H105),
 C106(H106), C108(H108), C113(H113), C112(H112), C111(H111), C110(H110),
 C109(H109), C114(H114), C115(H115), C116(H116), C117(H117), C118(H118),
 C119(H119), C120(H120), C121(H121), C122(H122), C123(H123), C124(H124),
 C125(H125)
5.d Fitted hexagon refined as free rotating group:
 C108(C113,C112,C111,C110,C109), C114(C115,C116,C117,C118,C119)
5.e Idealised Me refined as rotating group:
 C82B(H82A,H82B,H82C), C81B(H81A,H81B,H81C), C80B(H80A,H80B,H80C), C80A(H80D,
 H80E,H80F), C82A(H82D,H82E,H82F), C81A(H81D,H81E,H81F)
;
_olex2_submission_special_instructions 'No special instructions were received'