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_4125555
_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         'C40 H65 B Fe O P3 Si, 0.33(C4 H10 O)'
_chemical_formula_sum            'C41.31 H68.26 B Fe O1.32 P3 Si'
_chemical_formula_weight         773.74
_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   geom
_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                78.666(2)
_cell_angle_beta                 78.736(2)
_cell_angle_gamma                62.016(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9056(7)
_cell_length_b                   11.3906(7)
_cell_length_c                   20.2061(14)
_cell_measurement_reflns_used    8836
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.07
_cell_measurement_theta_min      2.40
_cell_volume                     2157.9(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.1299
_diffrn_reflns_av_unetI/netI     0.0946
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            46776
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.397
_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    0.519
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1228 before and 0.0301 after correction. The Ratio of minimum to maximum transmission is 0.7394. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_description       plate
_exptl_crystal_F_000             833
_exptl_crystal_size_max          0.268
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.132
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.841
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     659
_refine_ls_number_reflns         8802
_refine_ls_number_restraints     196
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1234
_refine_ls_R_factor_gt           0.0716
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0774P)^2^+2.9498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1618
_refine_ls_wR_factor_ref         0.1870
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5681
_reflns_number_total             8802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12444_si_002.cif
_cod_data_source_block           compound6
_cod_depositor_comments
'Adding full bibliography for 4125551--4125555.cif.'
_cod_database_code               4125555
_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. Uiso/Uaniso restraints and constraints
Uanis(C40B) = Uanis(C38A)
3. Rigid body (RIGU) restrains
 C25B, C25A, C23B, C23A, C24B, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31B, C31A, C29B, C29A, C30B, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35A, C37C, C35B, C37B, C36A, C36B, C36C, C35C, C37A, C32, P3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si1A, C40A, C39A, C38A, C40B, Si1B, C38B, C39B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C38A, O1B, Si1A, C40A, C39B, C40B, Si1B, O1A, C38B, C39A, C41, O2,
 C43, C42, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 1*[Sof(C35A)+Sof(H35A)+Sof(C36A)+Sof(H36A)+Sof(H36B)+Sof(H36C)+Sof(C37A)+
 Sof(H37G)+Sof(H37H)+Sof(H37I)]+1*[Sof(C35B)+Sof(H35B)+Sof(C37B)+Sof(H37D)+
 Sof(H37E)+Sof(H37F)+Sof(C36B)+Sof(H36D)+Sof(H36E)+Sof(H36F)]+1*[Sof(C37C)+
 Sof(H37A)+Sof(H37B)+Sof(H37C)+Sof(C36C)+Sof(H36G)+Sof(H36H)+Sof(H36I)+
 Sof(C35C)+Sof(H35C)]=1 with esd of 0.001
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(O1B)=Sof(Si1B)=Sof(C38B)=Sof(H38D)=Sof(H38E)=
 Sof(H38F)=Sof(C39B)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40B)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=1-FVAR(1)
 Sof(O2)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=0.5*FVAR(2)
 Sof(O1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 Sof(Si1A)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C39A)=Sof(H39A)=
 Sof(H39B)=Sof(H39C)=FVAR(1)
 Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37A)=
 Sof(H37G)=Sof(H37H)=Sof(H37I)=FVAR(2)
 Sof(C35B)=Sof(H35B)=Sof(C37B)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C36B)=
 Sof(H36D)=Sof(H36E)=Sof(H36F)=FVAR(3)
 Sof(C37C)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C36C)=Sof(H36G)=Sof(H36H)=
 Sof(H36I)=Sof(C35C)=Sof(H35C)=FVAR(4)
 Sof(C29B)=Sof(H29B)=Sof(C31B)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C30B)=
 Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(5)
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=
 Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(5)
 Sof(C25B)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C24B)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C23B)=Sof(H23B)=1-FVAR(6)
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25A)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=FVAR(6)
5.a Ternary CH refined with riding coordinates:
 C26(H26), C32(H32), C20(H20), C29A(H29A), C35A(H35A), C35B(H35B), C29B(H29B),
 C23A(H23A), C23B(H23B), C35C(H35C)
5.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C1B(H1BA,H1BB), C43(H43A,H43B), C42(H42A,H42B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C10(H10), C5(H5), C11(H11), C9(H9), C3(H3), C4(H4), C15(H15),
 C18(H18), C17(H17), C16(H16), C6(H6)
5.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C28(H28A,H28B,H28C), C21(H21A,H21B,H21C), C33(H33A,H33B,
 H33C), C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C30A(H30A,H30B,H30C),
 C31A(H31A,H31B,H31C), C38A(H38A,H38B,H38C), C40A(H40A,H40B,H40C), C38B(H38D,
 H38E,H38F), C39A(H39A,H39B,H39C), C39B(H39D,H39E,H39F), C40B(H40D,H40E,H40F),
 C37C(H37A,H37B,H37C), C37B(H37D,H37E,H37F), C36A(H36A,H36B,H36C), C36B(H36D,
 H36E,H36F), C36C(H36G,H36H,H36I), C31B(H31D,H31E,H31F), C30B(H30D,H30E,H30F),
 C25B(H25A,H25B,H25C), C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F), C25A(H25D,
 H25E,H25F), C37A(H37G,H37H,H37I), C44(H44A,H44B,H44C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              64625
_shelx_hkl_checksum              53109
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'