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_4125552
_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         'C41 H64.09 B Fe0.9 K O2 P2.7, 0.1(Fe P3)'
_chemical_formula_sum            'C41 H64.03 B Fe K O2 P3'
_chemical_formula_weight         787.61
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.987(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.965(2)
_cell_length_b                   19.074(3)
_cell_length_c                   16.191(2)
_cell_measurement_reflns_used    9991
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.69
_cell_measurement_theta_min      2.38
_cell_volume                     4484.6(11)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.97
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0724
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            85220
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.138
_diffrn_reflns_theta_min         2.498
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.567
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6519
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0778 before and 0.0612 after correction. The Ratio of minimum to maximum transmission is 0.8746. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1684
_exptl_crystal_size_max          0.268
_exptl_crystal_size_mid          0.208
_exptl_crystal_size_min          0.201
_refine_diff_density_max         2.398
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         7998
_refine_ls_number_restraints     239
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1263
_refine_ls_R_factor_gt           0.0920
_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^)+(0.1780P)^2^+14.7210P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2679
_refine_ls_wR_factor_ref         0.3062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5688
_reflns_number_total             7998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12444_si_002.cif
_cod_data_source_block           compound3
_cod_depositor_comments
'Adding full bibliography for 4125551--4125555.cif.'
_cod_database_code               4125552
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H,H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C41-O2 \\sim O2-C38
 with sigma of 0.02
 C40-C41 \\sim C39-C38
 with sigma of 0.02
 C41A-O2A \\sim O2A-C38A
 with sigma of 0.02
 C40A-C41A \\sim C39A-C38A
 with sigma of 0.02
 C40A-C41A \\sim C40-C41
 with sigma of 0.02
 C39-C38 \\sim C38A-C39A
 with sigma of 0.02
 C41-O2 \\sim O2A-C41A
 with sigma of 0.02
 C38A-O2A \\sim C38-O2
 with sigma of 0.02
 C40-C39 \\sim C40A-C39A
 with sigma of 0.02
 O2-C40 \\sim O2A-C40A
 with sigma of 0.02
 C38-C40 \\sim C38A-C40A
 with sigma of 0.02
 C39A-C41A \\sim C39-C41
 with sigma of 0.02
 C40-O2 \\sim C40A-O2A
 with sigma of 0.02
 C41-C38 \\sim C41A-C38A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C7, C2, C6, C3, C5, C4, C4AA, C5AA, C7AA, C0AA, C2AA, C1AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C008, C00I, C00P, C00R, C00S, C6AA, C9, C11, C12, C10, C13, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P6, Fe2, P4, P5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C41, C38, C40, C39, O2A, C41A, C40A, C39A, C38A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Fe2)=Sof(P6)=Sof(P5)=Sof(P4)=1-FVAR(1)
 Sof(Fe1)=Sof(P1)=Sof(P2)=Sof(P3)=FVAR(1)
 Sof(C4AA)=Sof(H4AA)=Sof(C5AA)=Sof(H5AA)=Sof(C7AA)=Sof(C0AA)=Sof(C2AA)=
 Sof(H2AA)=Sof(C1AA)=Sof(H1AA)=1-FVAR(2)
 Sof(C7)=Sof(C2)=Sof(C6)=Sof(H6)=Sof(H1A)=Sof(C3)=Sof(H3)=Sof(C5)=Sof(H5)=
 Sof(C4)=Sof(H4)=FVAR(2)
 Sof(C9)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C10)=Sof(H10)=Sof(C13)=
 Sof(H13)=Sof(C8)=1-FVAR(3)
 Sof(C008)=Sof(C00I)=Sof(H00I)=Sof(C00P)=Sof(H00P)=Sof(C00R)=Sof(H00R)=
 Sof(C00S)=Sof(H00S)=Sof(C6AA)=Sof(H1B)=FVAR(3)
 Sof(O2A)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=1-FVAR(4)
 Sof(O2)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), B1(H1B), B1(H1A), C26(H26), C29(H29), C32(H32), C35(H35)
5.b Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C38(H38A,H38B), C40(H40A,H40B), C39(H39A,H39B), C41A(H41C,
 H41D), C40A(H40C,H40D), C39A(H39C,H39D), C38A(H38C,H38D)
5.c Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00P(H00P), C00R(H00R), C00S(H00S), C18(H18), C17(H17), C16(H16),
 C15(H15), C6(H6), C3(H3), C5(H5), C4(H4), C4AA(H4AA), C5AA(H5AA), C2AA(H2AA),
 C1AA(H1AA), C11(H11), C12(H12), C10(H10), C13(H13)
5.d Fitted hexagon refined as free rotating group:
 C008(C00I,C00P,C00R,C00S,C6AA), C19(C18,C17,C16,C15,C14), C4AA(C5AA,C7AA,C0AA,
 C2AA,C1AA)
5.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C22(H22A,H22B,
 H22C), C30(H30A,H30B,H30C), C34(H34A,H34B,H34C), C28(H28A,H28B,H28C), C37(H37A,
 H37B,H37C), C36(H36A,H36B,H36C), C33(H33A,H33B,H33C), C27(H27A,H27B,H27C),
 C31(H31A,H31B,H31C)
;
_shelx_res_checksum              58876
_shelx_hkl_checksum              92284
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'