Iron-catalyzed asymmetric hydrosilylation of ketones
Ziqing Zuo; Lei Zhang; Xuebing Leng; Zheng Huang; Chem.Commun. 51 (2015) 5073–; doi:10.1039/C5cc00612K

data_7116740
_publ_section_title
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 Iron-catalyzed asymmetric hydrosilylation of ketones
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_journal_name_full               Chem.Commun.
_journal_page_first              5073
_journal_paper_doi               10.1039/C5cc00612K
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C47 H45 Br2 Fe N3 O'
_chemical_formula_sum            'C47 H45 Br2 Fe N3 O'
_chemical_formula_weight         883.53
_chemical_name_systematic
;
 ?
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_space_group_crystal_system      tetragonal
_space_group_IT_number           75
_space_group_name_Hall           'P 4'
_space_group_name_H-M_alt        'P 4'
_symmetry_space_group_name_Hall  'P 4'
_symmetry_space_group_name_H-M   'P 4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
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2015-01-20 deposited with the CCDC.
2015-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   33.2315(4)
_cell_length_b                   33.2315(4)
_cell_length_c                   18.2906(3)
_cell_measurement_reflns_used    9948
_cell_measurement_temperature    130
_cell_measurement_theta_max      68.674
_cell_measurement_theta_min      2.659
_cell_volume                     20198.9(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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 (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1082
_diffrn_reflns_av_unetI/netI     0.1085
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            112205
_diffrn_reflns_point_group_measured_fraction_full 0.921
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.753
_diffrn_reflns_theta_min         1.329
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.490
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.3163
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1473 before and 0.0873 after correction.
The Ratio of minimum to maximum transmission is 0.4199.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             7232
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.258
_refine_diff_density_min         -1.201
_refine_diff_density_rms         0.123
_refine_ls_abs_structure_details
;
 Flack x determined using 8368 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.082(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1953
_refine_ls_number_reflns         34361
_refine_ls_number_restraints     752
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0978
_refine_ls_R_factor_gt           0.0714
_refine_ls_shift/su_max          0.046
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1013P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1873
_refine_ls_wR_factor_ref         0.2029
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.840
_reflns_Friedel_fraction_max     0.811
_reflns_number_gt                24164
_reflns_number_total             34361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc00612k2_a.cif
_cod_data_source_block           cu_dm14700_0m
_cod_original_cell_volume        20198.9(6)
_cod_database_code               7116740
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.534
_shelx_estimated_absorpt_t_min   0.400
_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
 C48-C11A
 1.52 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C10A \\sim C11A \\sim C48 \\sim C13A \\sim C12A: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.08
C42 \\sim C47 \\sim C46 \\sim C45 \\sim C44 \\sim C43: within 1.7A with sigma
of 0.005 and sigma for terminal atoms of 0.08
C35A \\sim C40A \\sim C39A \\sim C38A \\sim C37A \\sim C36A: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.08
C36B \\sim C37B \\sim C38B \\sim C39B \\sim C40B \\sim C41B: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.08
C42B \\sim C43B \\sim C44B \\sim C45B \\sim C46B \\sim C47B: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.08
C23B \\sim C28B \\sim C27B \\sim C26B \\sim C25B \\sim C24B: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.08
C42C \\sim C43C \\sim C44C \\sim C45C \\sim C46C \\sim C47C: within 1.7A with
sigma of 0.005 and sigma for terminal atoms of 0.08
C48 \\sim C11A \\sim C13A \\sim C12A: within 1.7A with sigma of 0.001 and sigma
for terminal atoms of 0.002
N3A \\sim C8A \\sim O1A \\sim C9A \\sim C10A: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C4A) \\sim Ueq,
Uanis(C3A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C8B)
\\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C24B) \\sim Ueq,
Uanis(C21C) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C44A) \\sim Ueq, Uanis(C43A)
\\sim Ueq, Uanis(C45A) \\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C41A) \\sim Ueq,
Uanis(C42A) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C38A) \\sim Ueq,
Uanis(C37A) \\sim Ueq, Uanis(C11C) \\sim Ueq, Uanis(C21B) \\sim Ueq,
Uanis(C19B) \\sim Ueq, Uanis(C40B) \\sim Ueq, Uanis(C38B) \\sim Ueq, Uanis(C6C)
\\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C20C) \\sim Ueq, Uanis(C42C) \\sim Ueq,
Uanis(C45C) \\sim Ueq, Uanis(C46C) \\sim Ueq, Uanis(C39C) \\sim Ueq,
Uanis(C41B) \\sim Ueq, Uanis(O1B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C12B)
\\sim Ueq, Uanis(C14B) \\sim Ueq, Uanis(C25C) \\sim Ueq, Uanis(C24C) \\sim Ueq,
Uanis(C16C) \\sim Ueq, Uanis(C15C) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.2
Uanis(C21C) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C27B)
\\sim Ueq, Uanis(C21B) \\sim Ueq, Uanis(C39A) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C19C)
\\sim Ueq, Uanis(C18C) \\sim Ueq, Uanis(C17C) \\sim Ueq, Uanis(C26C) \\sim Ueq,
Uanis(C20B) \\sim Ueq, Uanis(C47B) \\sim Ueq, Uanis(C45B) \\sim Ueq,
Uanis(C33C) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C7A)
\\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C9A) \\sim Ueq: with sigma of 0.002 and
sigma for terminal atoms of 0.2
Uanis(C21C) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C21B)
\\sim Ueq, Uanis(C30A) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(C21) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of
0.0002
Uanis(C48) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.0002
4.a Ternary CH refined with riding coordinates:
 C10(H10), C22(H22), C35(H35), C10B(H10B), C22B(H22B), C35B(H35B), C10C(H10C),
 C22C(H22C), C35C(H35C), C10A(H10A), C21A(H21J), C34A(H34A)
4.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9B(H9BA,H9BB), C9C(H9CA,H9CB), C9A(H9AA,H9AB)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C17(H17), C19(H19), C24(H24), C25(H25), C26(H26),
 C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C37(H37),
  C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47), C4B(H4B), C5B(H5B), C6B(H6B), C17B(H17B), C19B(H19B),
 C24B(H24B), C25B(H25B), C26B(H26B), C27B(H27B), C28B(H28B), C30B(H30B),
 C31B(H31B), C32B(H32B), C33B(H33B), C34B(H34B), C37B(H37B), C38B(H38B),
 C39B(H39B), C40B(H40B), C41B(H41B), C43B(H43B), C44B(H44B), C45B(H45B),
 C46B(H46B), C47B(H47B), C4C(H4C), C5C(H5C), C6C(H6C), C17C(H17C), C19C(H19C),
 C24C(H24C), C25C(H25C), C26C(H26C), C27C(H27C), C28C(H28C), C30C(H30C),
 C31C(H31C), C32C(H32C), C33C(H33C), C34C(H34C), C37C(H37C), C38C(H38C),
 C39C(H39C), C40C(H40C), C41C(H41C), C43C(H43C), C44C(H44C), C45C(H45C),
 C46C(H46C), C47C(H47C), C4A(H4A), C5A(H5A), C6A(H6A), C16A(H16A), C18A(H18A),
 C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C29A(H29A),
 C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C36A(H36A), C37A(H37A),
 C38A(H38A), C39A(H39A), C40A(H40A), C42A(H42A), C43A(H43A), C44A(H44A),
 C45A(H45A), C46A(H46A)
4.d Fitted hexagon refined as free rotating group:
 C42C(C43C,C44C,C45C,C46C,C47C)
4.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C21(H21A,H21B,H21C), C1B(H1BA,H1BB,H1BC), C12B(H12D,H12E,H12F),
 C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F), C21B(H21D,H21E,H21F), C1C(H1CA,
 H1CB,H1CC), C12C(H12G,H12H,H12I), C13C(H13G,H13H,H13I), C14C(H14G,H14H,H14I),
 C21C(H21G,H21H,H21I), C1A(H1AA,H1AB,H1AC), C12A(H12J,H12K,H12L), C13A(H13J,
 H13K,H13L), C20A(H20A,H20B,H20C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              40636
_shelx_hkl_checksum              8450
_olex2_submission_special_instructions 'No special instructions were received'