CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site.
Deegan, Meaghan M.; Peters, Jonas C.; Journal of the American Chemical Society 139 (2017) 2561–2564; doi:10.1021/jacs.6b12444

data_4125553
_publ_section_title
;
 CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a
 Single Fe Site.
;
_journal_issue                   7
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2561
_journal_page_last               2564
_journal_paper_doi               10.1021/jacs.6b12444
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C45 H71 B Fe K O3 P3, 2(C4 H8 O)'
_chemical_formula_sum            'C53 H87 B Fe K O5 P3'
_chemical_formula_weight         1002.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.24 svn.r3356 for OlexSys, GUI svn.r5267)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.191(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2309(19)
_cell_length_b                   23.142(4)
_cell_length_c                   20.143(3)
_cell_measurement_reflns_used    9451
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.02
_cell_measurement_theta_min      2.37
_cell_volume                     5194.1(15)
_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      100.01
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0733
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            340633
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         36.347
_diffrn_reflns_theta_min         2.371
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0704 before and 0.0565 after correction. The Ratio of minimum to maximum transmission is 0.9611. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.918
_refine_diff_density_min         -0.981
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     799
_refine_ls_number_reflns         25208
_refine_ls_number_restraints     327
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0710
_refine_ls_R_factor_gt           0.0458
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0539P)^2^+3.8483P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1097
_refine_ls_wR_factor_ref         0.1208
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19141
_reflns_number_total             25208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12444_si_002.cif
_cod_data_source_block           compound4
_cod_depositor_comments
'Adding full bibliography for 4125551--4125555.cif.'
_cod_database_code               4125553
_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
 O5B-C49B \\sim O5C-C49C \\sim O5A-C49A
 with sigma of 0.02
 C49A-C50A \\sim C49B-C50B \\sim C49C-C50C
 with sigma of 0.02
 C50A-C51A \\sim C50B-C51B \\sim C50C-C51C
 with sigma of 0.02
 C52B-O5B \\sim C52A-O5A \\sim C52C-O5C
 with sigma of 0.02
 C51B-C52B \\sim C51A-C52A \\sim C51C-C52C
 with sigma of 0.02
 O5B-C51A \\sim O5A-C51B \\sim O5C-C51C
 with sigma of 0.02
 C52B-C50A \\sim C52A-C50B \\sim C52C-C50C
 with sigma of 0.02
 C51C-C49C \\sim C51B-C49B \\sim C51A-C49A
 with sigma of 0.02
 C50C-O5C \\sim C50B-O5B \\sim C50A-O5A
 with sigma of 0.02
 C49C-C52C \\sim C49A-C52A \\sim C49B-C52B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O4B) = Uanis(O4A)
Uanis(O5C) = Uanis(O5A) = Uanis(O5B)
Uanis(C50A) = Uanis(C50B)
4. Rigid body (RIGU) restrains
 O4A, C45A, C46A, C47A, C48A, O4B, C45B, C46B, C47B, C48B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5A, C52A, C51A, C49A, C50A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49B, C50B, C51B, C52B, O5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5A, C52A, C51A, C49A, C50A, C49B, C50B, C51B, C52B, O5B, C52C, C51C, C50C,
 C49C, O5C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3A, O2A, C37A, C44A, C38A, C40A, C41A, C39A, C43A, C42A, C39B, C41B, C42B,
 C43B, C44B, O3B, C40B, O2B, C37B, C38B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O4B, C45B, C46B, C47B, C48B} sigma for 1-2: 0.01, 1-3: 0.02
{O4A, C48A, C47A, C46A, C45A} sigma for 1-2: 0.01, 1-3: 0.02
as
{O4A, C45A, C46A, C47A, C48A}
6. Others
 1*[Sof(O5A)+Sof(C52A)+Sof(H52A)+Sof(H52B)+Sof(C51A)+Sof(H51A)+Sof(H51B)+
 Sof(C49A)+Sof(H49A)+Sof(H49B)+Sof(C50A)+Sof(H50A)+Sof(H50B)]+1*[Sof(C49B)+
 Sof(H49C)+Sof(H49D)+Sof(C50B)+Sof(H50C)+Sof(H50D)+Sof(C51B)+Sof(H51C)+
 Sof(H51D)+Sof(C52B)+Sof(H52C)+Sof(H52D)+Sof(O5B)]+1*[Sof(C52C)+Sof(H52E)+
 Sof(H52F)+Sof(C51C)+Sof(H51E)+Sof(H51F)+Sof(C50C)+Sof(H50E)+Sof(H50F)+
 Sof(C49C)+Sof(H49E)+Sof(H49F)+Sof(O5C)]=1 with esd of 0.0001
 Sof(C39B)=Sof(H39C)=Sof(H39D)=Sof(C41B)=Sof(H41C)=Sof(H41D)=Sof(C42B)=
 Sof(H42C)=Sof(H42D)=Sof(C43B)=Sof(H43C)=Sof(H43D)=Sof(C44B)=Sof(H44C)=
 Sof(H44D)=Sof(O3B)=Sof(C40B)=Sof(H40C)=Sof(H40D)=Sof(O2B)=Sof(C37B)=Sof(H37C)=
 Sof(H37D)=Sof(C38B)=Sof(H38C)=Sof(H38D)=1-FVAR(1)
 Sof(O3A)=Sof(O2A)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C44A)=Sof(H44A)=Sof(H44B)=
 Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C41A)=
 Sof(H41A)=Sof(H41B)=Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(C43A)=Sof(H43A)=
 Sof(H43B)=Sof(C42A)=Sof(H42A)=Sof(H42B)=FVAR(1)
 Sof(O5A)=Sof(C52A)=Sof(H52A)=Sof(H52B)=Sof(C51A)=Sof(H51A)=Sof(H51B)=
 Sof(C49A)=Sof(H49A)=Sof(H49B)=Sof(C50A)=Sof(H50A)=Sof(H50B)=FVAR(2)
 Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=
 Sof(H51C)=Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=Sof(O5B)=FVAR(3)
 Sof(C52C)=Sof(H52E)=Sof(H52F)=Sof(C51C)=Sof(H51E)=Sof(H51F)=Sof(C50C)=
 Sof(H50E)=Sof(H50F)=Sof(C49C)=Sof(H49E)=Sof(H49F)=Sof(O5C)=FVAR(4)
 Sof(O4B)=Sof(C45B)=Sof(H45C)=Sof(H45D)=Sof(C46B)=Sof(H46C)=Sof(H46D)=
 Sof(C47B)=Sof(H47C)=Sof(H47D)=Sof(C48B)=Sof(H48C)=Sof(H48D)=1-FVAR(5)
 Sof(O4A)=Sof(C45A)=Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(H46A)=Sof(H46B)=
 Sof(C47A)=Sof(H47A)=Sof(H47B)=Sof(C48A)=Sof(H48A)=Sof(H48B)=FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C25(H25), C35(H35), C28(H28), C32(H32)
7.b Secondary CH2 refined with riding coordinates:
 C37A(H37A,H37B), C44A(H44A,H44B), C38A(H38A,H38B), C40A(H40A,H40B), C41A(H41A,
 H41B), C39A(H39A,H39B), C43A(H43A,H43B), C42A(H42A,H42B), C39B(H39C,H39D),
 C41B(H41C,H41D), C42B(H42C,H42D), C43B(H43C,H43D), C44B(H44C,H44D), C40B(H40C,
 H40D), C37B(H37C,H37D), C38B(H38C,H38D), C52A(H52A,H52B), C51A(H51A,H51B),
 C49A(H49A,H49B), C50A(H50A,H50B), C45A(H45A,H45B), C46A(H46A,H46B), C47A(H47A,
 H47B), C48A(H48A,H48B), C49B(H49C,H49D), C50B(H50C,H50D), C51B(H51C,H51D),
 C52B(H52C,H52D), C45B(H45C,H45D), C46B(H46C,H46D), C47B(H47C,H47D), C48B(H48C,
 H48D), C52C(H52E,H52F), C51C(H51E,H51F), C50C(H50E,H50F), C49C(H49E,H49F)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C8(H8), C17(H17), C11(H11), C9(H9), C4(H4), C10(H10), C5(H5),
 C16(H16), C15(H15), C14(H14)
7.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C36(H36A,H36B,H36C), C23(H23A,H23B,H23C), C21(H21A,H21B,
 H21C), C29(H29A,H29B,H29C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C34(H34A,H34B,H34C),
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              10045
_shelx_hkl_checksum              95378
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'