Identification and Reactivity of Cyclometalated Iron(II) Intermediates in Triazole-Directed Iron-Catalyzed C-H Activation.
Boddie, Theresa E.; Carpenter, Stephanie H.; Baker, Tessa M.; DeMuth, Joshua C.; Cera, Gianpiero; Brennessel, William W.; Ackermann, Lutz; Neidig, Michael L.; Journal of the American Chemical Society 141 (2019) 12338–12345; doi:10.1021/jacs.9b05269

data_4128620
_publ_section_title
;
 Identification and Reactivity of Cyclometalated Iron(II) Intermediates in
 Triazole-Directed Iron-Catalyzed C-H Activation.
;
_journal_issue                   31
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12338
_journal_page_last               12345
_journal_paper_doi               10.1021/jacs.9b05269
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C114 H118 Fe2 Mg N8 O5 P4, C16 H32 Br1.55 Cl0.45 Mg O4, C16 H32 Br1.26 Cl0.74 Mg O4'
_chemical_formula_sum            'C146 H182 Br2.81 Cl1.19 Fe2 Mg3 N8 O13 P4'
_chemical_formula_weight         2832.01
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-03-12
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                105.2570(10)
_cell_angle_beta                 98.2230(10)
_cell_angle_gamma                116.4860(10)
_cell_formula_units_Z            2
_cell_length_a                   20.9654(3)
_cell_length_b                   22.0142(3)
_cell_length_c                   24.3610(2)
_cell_measurement_reflns_used    50736
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      77.2180
_cell_measurement_theta_min      2.4570
_cell_volume                     9256.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -65.00  19.00   0.50   10.58    --  -49.87  63.00 -45.00  168
  2  \w    -12.00  13.00   0.50   10.58    --  -49.87  19.00 -90.00   50
  3  \w    -50.00 -17.00   0.50   10.58    --  -49.87  19.00 -90.00   66
  4  \w    -78.00 -10.00   0.50   10.58    --  -49.87 125.00  60.00  136
  5  \w   -116.00 -35.00   0.50   10.58    --  -49.87 -63.00 177.00  162
  6  \w     35.00 101.00   0.50   10.58    --   49.87  63.00 -45.00  132
  7  \w     31.00  62.00   0.50   10.58    --   49.87-125.00  30.00   62
  8  \w     28.00  55.00   0.50   10.58    --   49.87 -63.00 177.00   54
  9  \w     42.00  95.00   0.50   10.58    --   49.87-125.00-150.00  106
 10  \w    -12.00  21.00   0.50   10.58    --   49.87 -63.00 177.00   66
 11  \w   -121.00 -82.00   0.50   10.58    --  -49.87-125.00 120.00   78
 12  \w    -80.00 -55.00   0.50   42.34    --  -84.25  63.00 -45.00   50
 13  \w    -60.00 -13.00   0.50   42.34    --  -84.25  45.00 120.00   94
 14  \w   -120.00 -91.00   0.50   42.34    --  -84.25 -63.00 177.00   58
 15  \w     91.00 177.00   0.50   42.34    --  105.75  63.00 -45.00  172
 16  \w     98.00 160.00   0.50   42.34    --  105.75  15.00-120.00  124
 17  \w    102.00 178.00   0.50   42.34    --  105.75  30.00 -60.00  152
 18  \w     90.00 127.00   0.50   42.34    --  105.75 -77.00   0.00   74
 19  \w     96.00 121.00   0.50   42.34    --  105.75-133.00  -7.63   50
 20  \w     79.00 106.00   0.50   42.34    --  105.75 -94.00  90.00   54
 21  \w     46.00  76.00   0.50   42.34    --  105.75 -63.00 177.00   60
 22  \w     39.00 127.00   0.50   42.34    --  105.75 -77.00 150.00  176
 23  \w     41.00  71.00   0.50   42.34    --  105.75 -30.00  60.00   60
 24  \w     33.00  79.00   0.50   42.34    --  105.75 -15.00  30.00   92
 25  \w     38.00  82.00   0.50   42.34    --  105.75 -15.00 -30.00   88
 26  \w     35.00 109.00   0.50   42.34    --  105.75 -94.00   0.00  148
 27  \w     47.00  87.00   0.50   42.34    --  105.75 -94.00 -60.00   80
 28  \w     34.00  87.00   0.50   42.34    --  105.75 -77.00   0.00  106
 29  \w     34.00  59.00   0.50   42.34    --  105.75 -30.00 -60.00   50
 30  \w     34.00  69.00   0.50   42.34    --  105.75 -30.00 -30.00   70
 31  \w     34.00  61.00   0.50   42.34    --  105.75 -30.00  30.00   54
 32  \w     36.00  61.00   0.50   42.34    --  105.75 -15.00  60.00   50
 33  \w     35.00  67.00   0.50   42.34    --  105.75 -15.00 120.00   64
 34  \w     37.00 109.00   0.50   42.34    --  105.75 -94.00 150.00  144
 35  \w     34.00  98.00   0.50   42.34    --  105.75 -94.00  60.00  128
 36  \w     38.00  63.00   0.50   42.34    --  105.75-133.00  -7.63   50
 37  \w     38.00 107.00   0.50   42.34    --  105.75 -94.00 -90.00  138
 38  \w     75.00 109.00   0.50   42.34    --  105.75 -94.00-150.00   68
 39  \w     35.00  68.00   0.50   42.34    --  105.75 -30.00-150.00   66
 40  \w     37.00  62.00   0.50   42.34    --  105.75 -15.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0670673000
_diffrn_orient_matrix_UB_12      0.0433968000
_diffrn_orient_matrix_UB_13      -0.0200736000
_diffrn_orient_matrix_UB_21      -0.0152155000
_diffrn_orient_matrix_UB_22      -0.0717791000
_diffrn_orient_matrix_UB_23      -0.0460842000
_diffrn_orient_matrix_UB_31      -0.0518131000
_diffrn_orient_matrix_UB_32      0.0064439000
_diffrn_orient_matrix_UB_33      -0.0469015000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0771
_diffrn_reflns_av_unetI/netI     0.0585
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            126419
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.229
_diffrn_reflns_theta_min         2.413
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.927
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68965
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange-red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.016
_exptl_crystal_description       needle
_exptl_crystal_F_000             2969
_exptl_crystal_size_max          0.693
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.023
_refine_diff_density_max         1.203
_refine_diff_density_min         -0.953
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1718
_refine_ls_number_reflns         38166
_refine_ls_number_restraints     168
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0953P)^2^+2.7896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1702
_refine_ls_wR_factor_ref         0.1797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29145
_reflns_number_total             38166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05269_si_003.cif
_cod_data_source_block           neijd01
_cod_database_code               4128620
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.236
_reflns_odcompleteness_completeness 98.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Br3, Cl3}
{Br4, Cl4}
{Br1, Cl1}
{Br2, Cl2}
{O4, O4"}
3. Restrained distances
 C11-C12 \\sim C11-C12'
 with sigma of 0.01
 C62-C63 \\sim C62-C63'
 with sigma of 0.01
 Mg2-O9 \\sim Mg2-O9"
 with sigma of 0.02
 Mg3-O10 \\sim Mg3-O10"
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O9 \\sim C127 \\sim C128 \\sim C129 \\sim C130: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04
C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C12) = Uanis(C12')
Uanis(C13) = Uanis(C13')
Uanis(C14) = Uanis(C14')
Uanis(C15) = Uanis(C15')
Uanis(C16) = Uanis(C16')
Uanis(C17) = Uanis(C17')
Uanis(C63) = Uanis(C63')
Uanis(C64) = Uanis(C64')
Uanis(C65) = Uanis(C65')
Uanis(C66) = Uanis(C66')
Uanis(C67) = Uanis(C67')
Uanis(C68) = Uanis(C68')
Uanis(O4) = Uanis(O4")
Uanis(C112) = Uanis(C12")
Uanis(C113) = Uanis(C13")
Uanis(C114) = Uanis(C14")
Uanis(O9) = Uanis(O9")
Uanis(C127) = Uanis(C27")
Uanis(C128) = Uanis(C28")
Uanis(C129) = Uanis(C29")
Uanis(C130) = Uanis(C30")
Uanis(Br1) = Uanis(Cl1)
Uanis(Br2) = Uanis(Cl2)
Uanis(O10) = Uanis(O10")
Uanis(C131) = Uanis(C31")
Uanis(C132) = Uanis(C32")
Uanis(C133) = Uanis(C33")
Uanis(C134) = Uanis(C34")
Uanis(Br3) = Uanis(Cl3)
Uanis(Br4) = Uanis(Cl4)
5. Same fragment restrains
{O4, C111, C112, C113, C114} sigma for 1-2: 0.02, 1-3: 0.04
as
{O4", C11", C12", C13", C14"}
{C11, C12', C13', C14', C15', C16', C17'} sigma for 1-2: 0.02, 1-3: 0.04
as
{C11, C12, C13, C14, C15, C16, C17}
{C62, C63', C64', C65', C66', C67', C68'} sigma for 1-2: 0.02, 1-3: 0.04
as
{C62, C63, C64, C65, C66, C67, C68}
{O9, C130, C129, C128, C127} sigma for 1-2: 0.02, 1-3: 0.04
as
{O9, C127, C128, C129, C130}
{O9, C127, C128, C129, C130} sigma for 1-2: 0.02, 1-3: 0.04
as
{O9", C27", C28", C29", C30"}
{O10, C134, C133, C132, C131} sigma for 1-2: 0.02, 1-3: 0.04
as
{O10, C131, C132, C133, C134}
{O10, C131, C132, C133, C134} sigma for 1-2: 0.02, 1-3: 0.04
as
{O10", C31", C32", C33", C34"}
6. Others
 Sof(H11M)=Sof(H11N)=Sof(C12')=Sof(C13')=Sof(H13')=Sof(C14')=Sof(H14')=
 Sof(C15')=Sof(H15')=Sof(C16')=Sof(H16')=Sof(C17')=Sof(H17')=1-FVAR(1)
 Sof(H11K)=Sof(H11L)=Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=FVAR(1)
 Sof(H62C)=Sof(H62D)=Sof(C63')=Sof(C64')=Sof(H64')=Sof(C65')=Sof(H65')=
 Sof(C66')=Sof(H66')=Sof(C67')=Sof(H67')=Sof(C68')=Sof(H68')=1-FVAR(2)
 Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=Sof(C66)=
 Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=FVAR(2)
 Sof(O4")=Sof(C11")=Sof(H11I)=Sof(H11J)=Sof(C12")=Sof(H12A)=Sof(H12B)=
 Sof(C13")=Sof(H13A)=Sof(H13B)=Sof(C14")=Sof(H14A)=Sof(H14B)=1-FVAR(3)
 Sof(O4)=Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(C112)=Sof(H11C)=Sof(H11D)=Sof(C113)=
 Sof(H11E)=Sof(H11F)=Sof(C114)=Sof(H11G)=Sof(H11H)=FVAR(3)
 Sof(O9")=Sof(C27")=Sof(H27A)=Sof(H27B)=Sof(C28")=Sof(H28A)=Sof(H28B)=
 Sof(C29")=Sof(H29A)=Sof(H29B)=Sof(C30")=Sof(H30A)=Sof(H30B)=1-FVAR(4)
 Sof(O9)=Sof(C127)=Sof(H12C)=Sof(H12D)=Sof(C128)=Sof(H12E)=Sof(H12F)=Sof(C129)=
 Sof(H12G)=Sof(H12H)=Sof(C130)=Sof(H13C)=Sof(H13D)=FVAR(4)
 Sof(O10")=Sof(C31")=Sof(H31A)=Sof(H31B)=Sof(C32")=Sof(H32A)=Sof(H32B)=
 Sof(C33")=Sof(H33A)=Sof(H33B)=Sof(C34")=Sof(H34A)=Sof(H34B)=1-FVAR(5)
 Sof(O10)=Sof(C131)=Sof(H13E)=Sof(H13F)=Sof(C132)=Sof(H13G)=Sof(H13H)=
 Sof(C133)=Sof(H13I)=Sof(H13J)=Sof(C134)=Sof(H13K)=Sof(H13L)=FVAR(5)
 Sof(Cl1)=1-FVAR(6)
 Sof(Br1)=FVAR(6)
 Sof(Cl2)=1-FVAR(7)
 Sof(Br2)=FVAR(7)
 Sof(Cl3)=1-FVAR(8)
 Sof(Br3)=FVAR(8)
 Sof(Cl4)=1-FVAR(9)
 Sof(Br4)=FVAR(9)
7.a Secondary CH2 refined with riding coordinates:
 C111(H11A,H11B), C112(H11C,H11D), C113(H11E,H11F), C114(H11G,H11H), C11"(H11I,
 H11J), C12"(H12A,H12B), C13"(H13A,H13B), C14"(H14A,H14B), C11(H11K,H11L),
 C11(H11M,H11N), C20(H20A,H20B), C21(H21A,H21B), C62(H62A,H62B), C62(H62C,H62D),
  C71(H71A,H71B), C72(H72A,H72B), C103(H10A,H10B), C104(H10C,H10D), C105(H10E,
 H10F), C106(H10G,H10H), C107(H10I,H10J), C108(H10K,H10L), C109(H10M,H10N),
 C110(H11O,H11P), C127(H12C,H12D), C128(H12E,H12F), C129(H12G,H12H), C130(H13C,
 H13D), C27"(H27A,H27B), C28"(H28A,H28B), C29"(H29A,H29B), C30"(H30A,H30B),
 C115(H11Q,H11R), C116(H11S,H11T), C117(H11U,H11V), C118(H11W,H11X), C119(H11Y,
 H), C120(H12I,H12J), C121(H12K,H12L), C122(H12M,H12N), C123(H12O,H12P),
 C124(H12Q,H12R), C125(H12S,H12T), C126(H12U,H12V), C131(H13E,H13F), C132(H13G,
 H13H), C133(H13I,H13J), C134(H13K,H13L), C31"(H31A,H31B), C32"(H32A,H32B),
 C33"(H33A,H33B), C34"(H34A,H34B), C135(H13M,H13N), C136(H13O,H13P), C137(H13Q,
 H13R), C138(H13S,H13T), C139(H13U,H13V), C140(H14C,H14D), C141(H14E,H14F),
 C142(H14G,H14H), C143(H14I,H14J), C144(H14K,H14L), C145(H14M,H14N), C146(H14O,
 H14P)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C13'(H13'), C14'(H14'), C15'(H15'), C16'(H16'), C17'(H17'),
  C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C29(H29), C30(H30),
 C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39),
  C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48),
 C49(H49), C50(H50), C51(H51), C53(H53), C54(H54), C55(H55), C56(H56), C61(H61),
  C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C64'(H64'), C65'(H65'),
 C66'(H66'), C67'(H67'), C68'(H68'), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C86(H86), C87(H87),
  C88(H88), C89(H89), C90(H90), C92(H92), C93(H93), C94(H94), C95(H95),
 C96(H96), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102)
7.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C69(H69A,H69B,H69C), C70(H70A,H70B,
 H70C)
;
_shelx_res_checksum              45909
_shelx_hkl_checksum              60091
_shelx_fab_checksum              86572
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.767
_oxdiff_exptl_absorpt_empirical_full_min 0.233