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_4125551
_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
'C168 H261 B4 Fe4 K8 O9 P12, 2.29(C6 H6), 2.41(C5 H12), 1(C4 H8 O)'
_chemical_formula_sum            'C197.83 H311.84 B4 Fe4 K8 O9.96 P12'
_chemical_formula_weight         3800.66
_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     direct
_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                 99.494(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8485(17)
_cell_length_b                   41.389(4)
_cell_length_c                   26.821(3)
_cell_measurement_reflns_used    9600
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.54
_cell_measurement_theta_min      2.26
_cell_volume                     20637(4)
_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    'SIR2004 (Burla et al., 2007)'
_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 0.999
_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  0.1391
_diffrn_reflns_av_unetI/netI     0.1137
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       55
_diffrn_reflns_limit_k_min       -55
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            376137
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.283
_diffrn_reflns_theta_min         2.133
_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    0.583
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1248 before and 0.0660 after correction. The Ratio of minimum to maximum transmission is 0.9401. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       block
_exptl_crystal_F_000             8138
_exptl_crystal_size_max          0.415
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.112
_refine_diff_density_max         2.416
_refine_diff_density_min         -1.222
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2408
_refine_ls_number_reflns         51181
_refine_ls_number_restraints     747
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.1605
_refine_ls_R_factor_gt           0.0950
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0331P)^2^+124.2417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1814
_refine_ls_wR_factor_ref         0.2029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32134
_reflns_number_total             51181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b12444_si_002.cif
_cod_data_source_block           compound2
_cod_depositor_comments
'Adding full bibliography for 4125551--4125555.cif.'
_cod_original_cell_volume        20638(3)
_cod_database_code               4125551
_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
 O10-C189 \\sim O5-C151
 with sigma of 0.02
 O10-C187 \\sim O5-C150
 with sigma of 0.02
 C189-C187 \\sim C151-C149
 with sigma of 0.02
 C194-C193 \\sim C190-C191
 with sigma of 0.02
 C194-C192 \\sim C192-C190
 with sigma of 0.02
 C193-C192 \\sim C192-C191
 with sigma of 0.02
 O11-C195 \\sim O5_$1-C151_$1
 with sigma of 0.02
 C195-C196 \\sim C151_$1-C150_$1
 with sigma of 0.02
 C196-C197 \\sim C150_$1-C149_$1
 with sigma of 0.02
 C149-C148 \\sim C197_$2-C198_$2
 with sigma of 0.02
 C148-O5 \\sim C198_$2-O11_$2
 with sigma of 0.02
 O11-C196 \\sim O5_$1-C150_$1
 with sigma of 0.02
 C195-C197 \\sim C151_$1-C149_$1
 with sigma of 0.02
 C196-C198 \\sim C150_$1-C148_$1
 with sigma of 0.02
 C197-O11 \\sim C149_$1-O5_$1
 with sigma of 0.02
 O10-C186 \\sim O5-C148
 with sigma of 0.02
 C186-C187 \\sim C148-C149
 with sigma of 0.02
 C189-C186 \\sim C151-C148
 with sigma of 0.02
 C181-C183 \\sim C183-C185
 with sigma of 0.02
 C188-C187 \\sim C150-C149
 with sigma of 0.02
 C189-C188 \\sim C150-C151
 with sigma of 0.02
 O10-C188 \\sim O5-C149
 with sigma of 0.02
 C188-C186 \\sim C150-C148
 with sigma of 0.02
 C182-C183 \\sim C183-C184
 with sigma of 0.02
 C181-C182 \\sim C185-C184
 with sigma of 0.02
 O12-C208 \\sim O5-C151
 with sigma of 0.02
 C208-C8AA \\sim C151-C150
 with sigma of 0.02
 C8AA-C206 \\sim C150-C149
 with sigma of 0.02
 C206-C205 \\sim C148-C149
 with sigma of 0.02
 O12-C8AA \\sim O5-C150
 with sigma of 0.02
 C208-C206 \\sim C151-C149
 with sigma of 0.02
 C8AA-C205 \\sim C151-C149
 with sigma of 0.02
 C206-O12 \\sim C150-O5
 with sigma of 0.02
 C205-C208 \\sim C148-C151
 with sigma of 0.02
 C180-C179 \\sim C180-C179
 with sigma of 0.02
 C180-C178 \\sim C180-C178
 with sigma of 0.02
 C179-C178 \\sim C179-C178
 with sigma of 0.02
 C179-C177 \\sim C179-C177
 with sigma of 0.02
 C178-C177 \\sim C178-C177
 with sigma of 0.02
 C213-C212 \\sim C179-C180
 with sigma of 0.02
 C213-C214 \\sim C179-C178
 with sigma of 0.02
 C179-C178 \\sim C178-C177
 with sigma of 0.02
 C213-C214 \\sim C214-C215
 with sigma of 0.02
 C177-C178 \\sim C215-C214
 with sigma of 0.02
 C214-C212 \\sim C178-C180
 with sigma of 0.02
 C177-C179 \\sim C215-C213
 with sigma of 0.02
 C178-C176 \\sim C178-C176
 with sigma of 0.02
 C177-C176 \\sim C177-C176
 with sigma of 0.02
 C176-C177 \\sim C216-C215
 with sigma of 0.02
 C176-C177 \\sim C179-C180
 with sigma of 0.02
 C216-C215 \\sim C213-C212
 with sigma of 0.02
 C216-C214 \\sim C176-C178
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C194 \\sim C192 \\sim C193 \\sim C190 \\sim C191 \\sim O11 \\sim C197 \\sim
C196 \\sim C198 \\sim C195: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C185 \\sim C183 \\sim C181 \\sim C184 \\sim C182 \\sim C189 \\sim O10 \\sim
C186 \\sim C188 \\sim C187: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
O12 \\sim C206 \\sim C8AA \\sim C208 \\sim C205 \\sim C199 \\sim C204 \\sim
C207 \\sim C202 \\sim C201 \\sim C200: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C180 \\sim C180: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C179 \\sim C179: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C178 \\sim C178: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C177 \\sim C177: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C180 \\sim C212: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C179 \\sim C213: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C178 \\sim C214: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C177 \\sim C215: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C177 \\sim C179 \\sim C178 \\sim C176 \\sim C180 \\sim C212 \\sim C213 \\sim
C214 \\sim C215 \\sim C216: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C176 \\sim C216: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C186) = Uanis(C185)
Uanis(C216) = Uanis(C176)
4. Rigid body (RIGU) restrains
 C194, C192, C193, C190, C191, O11, C197, C196, C198, C195
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C185, C183, C181, C184, C182, C189, O10, C186, C188, C187
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O12, C206, C8AA, C208, C205, C199, C204, C207, C202, C201, C200
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C146, C146, C145, C147, C211, C210
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C146, C145, C147, C211, C210, C209
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C177, C177, C179, C179, C178, C178, C176, C176, C180, C180
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C177, C179, C178, C176, C180, C212, C213, C214, C215, C216
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C211)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C210)=Sof(H21G)=Sof(H21H)=
 Sof(H21I)=Sof(C209)=Sof(H209)=1-FVAR(1)
 Sof(C146)=Sof(H146)=Sof(C145)=Sof(H14Q)=Sof(H14R)=Sof(H14S)=Sof(C147)=
 Sof(H14T)=Sof(H14U)=Sof(H14V)=FVAR(1)
 Sof(C189)=Sof(H18P)=Sof(H18Q)=Sof(O10)=Sof(C186)=Sof(H18R)=Sof(H18S)=
 Sof(C188)=Sof(H18T)=Sof(H18U)=Sof(C187)=Sof(H18V)=Sof(H18W)=Sof(C212)=
 Sof(H21J)=Sof(H21K)=Sof(H21L)=Sof(C213)=Sof(H21M)=Sof(H21N)=Sof(C214)=
 Sof(H21O)=Sof(H21P)=Sof(C215)=Sof(H21Q)=Sof(H21R)=Sof(C216)=Sof(H21S)=
 Sof(H21T)=Sof(H21U)=1-FVAR(2)
 Sof(C177)=Sof(H17A)=Sof(H17B)=Sof(C179)=Sof(H17C)=Sof(H17D)=Sof(C178)=
 Sof(H17E)=Sof(H17F)=Sof(C176)=Sof(H17G)=Sof(H17H)=Sof(H17I)=Sof(C180)=
 Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C185)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C183)=Sof(H18G)=Sof(H18H)=Sof(C181)=Sof(H18I)=Sof(H18J)=Sof(H18K)=
 Sof(C184)=Sof(H18L)=Sof(H18M)=Sof(C182)=Sof(H18N)=Sof(H18O)=FVAR(2)
 Sof(O11)=Sof(C197)=Sof(H19M)=Sof(H19N)=Sof(C196)=Sof(H19O)=Sof(H19P)=
 Sof(C198)=Sof(H19Q)=Sof(H19R)=Sof(C195)=Sof(H19S)=Sof(H19T)=1-FVAR(3)
 Sof(C194)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C192)=Sof(H19D)=Sof(H19E)=
 Sof(C193)=Sof(H19F)=Sof(H19G)=Sof(C190)=Sof(H19H)=Sof(H19I)=Sof(H19J)=
 Sof(C191)=Sof(H19K)=Sof(H19L)=FVAR(3)
 Sof(C199)=Sof(H199)=Sof(C204)=Sof(H204)=Sof(C207)=Sof(H207)=Sof(C202)=
 Sof(H202)=Sof(C201)=Sof(H201)=Sof(C200)=Sof(H200)=0.7*(1-FVAR(5))
 Sof(O12)=Sof(C206)=Sof(H20A)=Sof(H20B)=Sof(C8AA)=Sof(H8AA)=Sof(H8AB)=
 Sof(C208)=Sof(H20C)=Sof(H20D)=Sof(C205)=Sof(H20E)=Sof(H20F)=0.7*FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C72(H72), C57(H57), C69(H69), C133(H133), C20(H20), C32(H32), C23(H23),
 C93(H93), C142(H142), C35(H35), C102(H102), C96(H96), C63(H63), C29(H29),
 C60(H60), C139(H139), C130(H130), C26(H26), C136(H136), C99(H99), C105(H105),
 C146(H146), C66(H66), C108(H108), C209(H209)
6.b Secondary CH2 refined with riding coordinates:
 C150(H15A,H15B), C148(H14D,H14E), C151(H15C,H15D), C162(H16A,H16B), C149(H14I,
 H14J), C04T(H04A,H04B), C163(H16C,H16D), C161(H16E,H16F), C156(H15E,H15F),
 C05B(H05A,H05B), C158(H15G,H15H), C152(H15I,H15J), C157(H15K,H15L), C05L(H05C,
 H05D), C155(H15M,H15N), C159(H15O,H15P), C05S(H05E,H05F), C153(H15Q,H15R),
 C160(H16G,H16H), C154(H15S,H15T), C177(H17A,H17B), C179(H17C,H17D), C178(H17E,
 H17F), C183(H18G,H18H), C184(H18L,H18M), C182(H18N,H18O), C192(H19D,H19E),
 C193(H19F,H19G), C191(H19K,H19L), C189(H18P,H18Q), C186(H18R,H18S), C188(H18T,
 H18U), C187(H18V,H18W), C197(H19M,H19N), C196(H19O,H19P), C198(H19Q,H19R),
 C195(H19S,H19T), C206(H20A,H20B), C8AA(H8AA,H8AB), C208(H20C,H20D), C205(H20E,
 H20F), C213(H21M,H21N), C214(H21O,H21P), C215(H21Q,H21R)
6.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C43(H43), C52(H52), C42(H42), C17(H17), C12(H12), C16(H16), C4(H4),
 C5(H5), C53(H53), C91(H91), C127(H127), C41(H41), C6(H6), C85(H85), C48(H48),
 C121(H121), C46(H46), C47(H47), C55(H55), C3(H3), C15(H15), C84(H84), C90(H90),
  C125(H125), C54(H54), C128(H128), C10(H10), C122(H122), C40(H40), C126(H126),
 C82(H82), C88(H88), C11(H11), C120(H120), C80(H80), C49(H49), C9(H9), C77(H77),
  C119(H119), C83(H83), C89(H89), C79(H79), C115(H115), C116(H116), C113(H113),
 C78(H78), C114(H114), C166(H166), C167(H167), C165(H165), C164(H164),
 C175(H175), C170(H170), C169(H169), C168(H168), C172(H172), C171(H171),
 C174(H174), C173(H173), C199(H199), C204(H204), C207(H207), C202(H202),
 C201(H201), C200(H200)
6.d Fitted hexagon refined as free rotating group:
 C199(C204,C207,C202,C201,C200)
6.e Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C97(H97A,H97B,H97C), C94(H94A,H94B,
 H94C), C135(H13A,H13B,H13C), C62(H62A,H62B,H62C), C30(H30A,H30B,H30C),
 C131(H13D,H13E,H13F), C58(H58A,H58B,H58C), C61(H61A,H61B,H61C), C36(H36A,H36B,
 H36C), C68(H68A,H68B,H68C), C65(H65A,H65B,H65C), C28(H28A,H28B,H28C),
 C100(H10A,H10B,H10C), C64(H64A,H64B,H64C), C141(H14A,H14B,H14C), C70(H70A,H70B,
 H70C), C37(H37A,H37B,H37C), C27(H27A,H27B,H27C), C137(H13G,H13H,H13I),
 C21(H21A,H21B,H21C), C98(H98A,H98B,H98C), C59(H59A,H59B,H59C), C71(H71A,H71B,
 H71C), C143(H14F,H14G,H14H), C101(H10D,H10E,H10F), C33(H33A,H33B,H33C),
 C31(H31A,H31B,H31C), C95(H95A,H95B,H95C), C134(H13J,H13K,H13L), C132(H13M,H13N,
 H13O), C22(H22A,H22B,H22C), C104(H10G,H10H,H10I), C34(H34A,H34B,H34C),
 C67(H67A,H67B,H67C), C103(H10J,H10K,H10L), C144(H14K,H14L,H14M), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C109(H10M,H10N,H10O), C140(H14N,H14O,H14P),
 C107(H10P,H10Q,H10R), C138(H13P,H13Q,H13R), C106(H10S,H10T,H10U), C110(H11A,
 H11B,H11C), C145(H14Q,H14R,H14S), C147(H14T,H14U,H14V), C211(H21D,H21E,H21F),
 C210(H21G,H21H,H21I), C176(H17G,H17H,H17I), C180(H18A,H18B,H18C), C185(H18D,
 H18E,H18F), C181(H18I,H18J,H18K), C194(H19A,H19B,H19C), C190(H19H,H19I,H19J),
 C212(H21J,H21K,H21L), C216(H21S,H21T,H21U)
;
_shelx_res_checksum              69765
_shelx_hkl_checksum              23776
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'