Taking Solution Proton NMR to Its Extreme: Prediction and Detection of a Hydride Resonance in an Intermediate-Spin Iron Complex.
Ott, Jonas C.; Wadepohl, Hubert; Enders, Markus; Gade, Lutz H.; Journal of the American Chemical Society 140 (2018) 17413–17417; doi:10.1021/jacs.8b11330

data_4133575
_publ_section_title
;
 Taking Solution Proton NMR to Its Extreme: Prediction and Detection of a
 Hydride Resonance in an Intermediate-Spin Iron Complex.
;
_journal_issue                   50
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17413
_journal_page_last               17417
_journal_paper_doi               10.1021/jacs.8b11330
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C45 H69 Fe N P2'
_chemical_formula_sum            'C45 H69 Fe N P2'
_chemical_formula_weight         741.80
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_jo23
_audit_creation_date             2018-08-23
_audit_creation_method
;
Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_audit_update_record
'24.09.2018 16:54:29 CEST UTC+02:00  encif 1.84'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.62428(11)
_cell_length_b                   23.62428(11)
_cell_length_c                   15.31409(13)
_cell_measurement_reflns_used    40541
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.8050
_cell_measurement_theta_min      5.0680
_cell_volume                     8546.89(9)
_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
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2014 (Giacovazzo et al., 2014)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    -15.00  12.00   1.00    8.00    --    0.00  57.00 -60.00   27
  2  \w    -55.00 -30.00   1.00    8.00    --    0.00 121.00 176.00   25
  3  \w    -19.00  22.00   1.00    8.00    --    0.00  57.00 120.00   41
  4  \w     19.00  69.00   1.00    8.00    --    0.00  57.00 -60.00   50
  5  \w     28.00  69.00   1.00    8.00    --    0.00  57.00 120.00   41
  6  \w     -8.00  68.00   1.00    8.00    --    0.00  77.00  30.00   76
  7  \w    -22.00  19.00   1.00    8.00    --   10.00  99.00-158.54   41
  8  \w    -25.00  13.00   1.00    8.00    --   18.00 107.00 -64.98   38
  9  \w    -19.00   6.00   1.00   15.00    --   30.00 112.00  76.68   25
 10  \w     -1.00  24.00   1.00   15.00    --   38.00  93.00-114.56   25
 11  \w      5.00  31.00   1.00   15.00    --   42.00  89.00  42.42   26
 12  \w      7.00  32.00   1.00   15.00    --   42.00  86.00 158.08   25
 13  \w      6.00  31.00   1.00   15.00    --   42.00  88.00-109.65   25
 14  \w     13.00  38.00   1.00   15.00    --   46.00  83.00-176.30   25
 15  \w     13.00  38.00   1.00   15.00    --   46.00  82.00 -87.02   25
 16  \w     12.00  38.00   1.00   15.00    --   46.00  84.00   8.10   26
 17  \w     18.00  43.00   1.00   15.00    --   50.00  80.00  62.79   25
 18  \w     17.00  42.00   1.00   15.00    --   50.00  82.00 -52.37   25
 19  \w     18.00  43.00   1.00   15.00    --   50.00  80.00 122.59   25
 20  \w     25.00  52.00   1.00   15.00    --   54.00  77.00-150.00   27
 21  \w    -14.00  74.00   1.00   15.00    --   54.00 -57.00 -30.00   88
 22  \w    -15.00  75.00   1.00   15.00    --   54.00 -57.00  60.00   90
 23  \w     27.00  53.00   1.00   15.00    --   54.00  77.00-180.00   26
 24  \w     76.00 102.00   1.00   15.00    --   54.00-125.00-120.00   26
 25  \w      1.00  96.00   1.00   15.00    --   54.00 -99.00-120.00   95
 26  \w     24.00  50.00   1.00   15.00    --   54.00  77.00  90.00   26
 27  \w     27.00  53.00   1.00   15.00    --   54.00  77.00-120.00   26
 28  \w     27.00  53.00   1.00   15.00    --   54.00  77.00 -90.00   26
 29  \w     31.00  60.00   1.00   15.00    --   54.00-125.00-120.00   29
 30  \w     24.00  50.00   1.00   15.00    --   54.00  77.00 150.00   26
 31  \w     29.00  55.00   1.00   15.00    --   58.00  77.00 -76.41   26
 32  \w     32.00  58.00   1.00   15.00    --   58.00  74.00 -54.25   26
 33  \w     30.00  56.00   1.00   15.00    --   58.00  77.00 -31.36   26
 34  \w     29.00  55.00   1.00   15.00    --   58.00  76.00 -15.49   26
 35  \w     99.00 125.00   1.00   15.00    --   58.00  77.00 -31.36   26
 36  \w     30.00  58.00   1.00   15.00    --   58.00  76.00  20.26   28
 37  \w     31.00  56.00   1.00   15.00    --   58.00  75.00  85.15   25
 38  \w    103.00 128.00   1.00   15.00    --   58.00  76.00  20.26   25
 39  \w     41.00  67.00   1.00   15.00    --   58.00  75.00 133.88   26
 40  \w     30.00  56.00   1.00   15.00    --   58.00  77.00 123.43   26
 41  \w     29.00  55.00   1.00   15.00    --   58.00  76.00-101.43   26
 42  \w     29.00  59.00   1.00   15.00    --   58.00  76.00  60.51   30
 43  \w     34.00  59.00   1.00   15.00    --   62.00  75.00 109.94   25
 44  \w     35.00  62.00   1.00   15.00    --   62.00  72.00-146.16   27
 45  \w     32.00  73.00   1.00   15.00    --   62.00  77.00 170.02   41
 46  \w     34.00  60.00   1.00   15.00    --   62.00  74.00-129.92   26
 47  \w     36.00  61.00   1.00   15.00    --   62.00  74.00 -84.10   25
 48  \w     35.00  61.00   1.00   15.00    --   62.00  75.00 -37.59   26
 49  \w     35.00  83.00   1.00   15.00    --   62.00  74.00  97.73   48
 50  \w     55.00 122.00   1.00   15.00    --   62.00  63.00  11.98   67
 51  \w     35.00  62.00   1.00   15.00    --   62.00  73.00 159.58   27
 52  \w     37.00  63.00   1.00   15.00    --   62.00  76.00 -21.85   26
 53  \w     40.00  66.00   1.00   15.00    --   66.00  70.00  91.73   26
 54  \w     38.00  91.00   1.00   15.00    --   66.00  74.00 156.25   53
 55  \w     41.00  67.00   1.00   15.00    --   70.00  76.00-129.41   26
 56  \w     41.00  71.00   1.00   15.00    --   70.00  75.00  25.18   30
 57  \w     65.00 117.00   1.00   15.00    --   70.00  66.00 109.17   52
 58  \w     46.00  85.00   1.00   15.00    --   74.00  74.00 -18.57   39
 59  \w     47.00  73.00   1.00   15.00    --   74.00  72.00 -55.13   26
 60  \w     52.00  92.00   1.00   15.00    --   74.00  70.00-179.18   40
 61  \w     52.00  92.00   1.00   15.00    --   74.00  72.00-114.02   40
 62  \w     55.00  84.00   1.00   15.00    --   78.00  64.00  38.86   29
 63  \w     51.00 143.00   1.00   15.00    --   78.00  72.00  91.46   92
 64  \w     49.00  79.00   1.00   15.00    --   78.00  75.00 159.12   30
 65  \w     48.00  74.00   1.00   15.00    --   78.00  77.00 -97.38   26
 66  \w     61.00 111.00   1.00   25.00    --   82.00  62.00 -82.45   50
 67  \w    113.00 148.00   1.00   25.00    --   82.00  61.00 -58.28   35
 68  \w     61.00 110.00   1.00   25.00    --   82.00  61.00 -58.28   49
 69  \w     62.00 101.00   1.00   25.00    --   82.00  43.00  51.12   39
 70  \w     54.00  87.00   1.00   25.00    --   82.00  74.00-148.29   33
 71  \w     64.00  93.00   1.00   25.00    --   82.00  58.00 142.72   29
 72  \w     64.00  90.00   1.00   25.00    --   86.00  67.00  82.98   26
 73  \w     60.00 106.00   1.00   25.00    --   86.00  71.00-135.44   46
 74  \w     65.00  99.00   1.00   25.00    --   86.00  58.00 152.37   34
 75  \w     66.00  93.00   1.00   25.00    --   86.00  48.00  20.27   27
 76  \w     63.00 148.00   1.00   25.00    --   86.00  48.00 -16.05   85
 77  \w     59.00 154.00   1.00   25.00    --   86.00  72.00  50.10   95
 78  \w     70.00  98.00   1.00   25.00    --   94.00  69.00 -43.65   28
 79  \w     70.00 121.00   1.00   25.00    --   98.00  73.00-179.17   51
 80  \w     86.00 165.00   1.00   25.00    --  108.00  64.00 -90.00   79
 81  \w     42.00 131.00   1.00   25.00    --  108.00 -64.00 -30.00   89
 82  \w     95.00 131.00   1.00   25.00    --  108.00 -64.00 150.00   36
 83  \w     47.00  73.00   1.00   25.00    --  108.00 -64.00 150.00   26
 84  \w     36.00  95.00   1.00   25.00    --  108.00 -92.00 -60.00   59
 85  \w    116.00 159.00   1.00   25.00    --  108.00  38.00-180.00   43
 86  \w     82.00 112.00   1.00   25.00    --  108.00  38.00-180.00   30
 87  \w     81.00 112.00   1.00   25.00    --  108.00-111.00 150.00   31
 88  \w     37.00  84.00   1.00   25.00    --  108.00 -92.00 150.00   47
 89  \w     37.00  76.00   1.00   25.00    --  108.00-111.00 150.00   39
 90  \w     86.00 112.00   1.00   25.00    --  108.00  64.00 150.00   26
 91  \w     86.00 111.00   1.00   25.00    --  108.00  64.00 120.00   25
 92  \w     86.00 165.00   1.00   25.00    --  108.00  64.00  60.00   79
 93  \w     86.00 164.00   1.00   25.00    --  108.00  64.00  30.00   78
 94  \w     86.00 113.00   1.00   25.00    --  108.00  64.00   0.00   27
 95  \w     78.00 104.00   1.00   25.00    --  108.00  77.00-150.00   26
 96  \w     85.00 173.00   1.00   25.00    --  108.00  64.00  90.00   88
 97  \w     78.00 104.00   1.00   25.00    --  108.00  77.00 -60.00   26
 98  \w     85.00 111.00   1.00   25.00    --  108.00  64.00-120.00   26
 99  \w     78.00 104.00   1.00   25.00    --  108.00  77.00 -30.00   26
100  \w     79.00 105.00   1.00   25.00    --  108.00  77.00 -90.00   26
101  \w     38.00 104.00   1.00   25.00    --  108.00 -92.00-150.00   66
102  \w     81.00 107.00   1.00   25.00    --  108.00  77.00-180.00   26
103  \w     79.00 174.00   1.00   25.00    --  108.00  77.00 120.00   95
104  \w     78.00 104.00   1.00   25.00    --  108.00  77.00  90.00   26
105  \w    114.00 157.00   1.00   25.00    --  108.00  77.00-120.00   43
106  \w     78.00 109.00   1.00   25.00    --  108.00  77.00-120.00   31
107  \w     77.00 103.00   1.00   25.00    --  108.00-111.00  90.00   26
108  \w     79.00 105.00   1.00   25.00    --  108.00  77.00  30.00   26
109  \w     78.00 176.00   1.00   25.00    --  108.00  77.00   0.00   98
110  \w     85.00 174.00   1.00   25.00    --  108.00  64.00-180.00   89
111  \w     85.00 174.00   1.00   25.00    --  108.00  64.00-150.00   89
112  \w     87.00 174.00   1.00   25.00    --  108.00  64.00 -60.00   87
113  \w     82.00 144.00   1.00   25.00    --  108.00  38.00 -60.00   62
114  \w     85.00 112.00   1.00   25.00    --  108.00-111.00   0.00   27
115  \w     46.00  72.00   1.00   25.00    --  108.00-111.00   0.00   26
116  \w     85.00 174.00   1.00   25.00    --  108.00  64.00 -30.00   89
117  \w    141.00 174.00   1.00   25.00    --  108.00  77.00 150.00   33
118  \w     78.00 104.00   1.00   25.00    --  108.00  77.00 150.00   26
119  \w     78.00 104.00   1.00   25.00    --  108.00  77.00  60.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0460111000
_diffrn_orient_matrix_UB_12      -0.0427126000
_diffrn_orient_matrix_UB_13      -0.0272123000
_diffrn_orient_matrix_UB_21      -0.0456711000
_diffrn_orient_matrix_UB_22      -0.0382351000
_diffrn_orient_matrix_UB_23      -0.0408831000
_diffrn_orient_matrix_UB_31      0.0070077000
_diffrn_orient_matrix_UB_32      0.0310700000
_diffrn_orient_matrix_UB_33      -0.0878127000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            96978
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.207
_diffrn_reflns_theta_min         3.439
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.746
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.663
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.153
_exptl_crystal_description       plate
_exptl_crystal_F_000             3216
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.434
_refine_diff_density_min         -0.386
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.019(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     495
_refine_ls_number_reflns         8243
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0395
_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^)+(0.0733P)^2^+5.7042P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1119
_reflns_Friedel_coverage         0.917
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                7871
_reflns_number_total             8243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11330_si_002.cif
_cod_data_source_block           ga_jo23
_cod_original_cell_volume        8546.89(11)
_cod_database_code               4133575
_audit_block_refno               3157
_audit_block_usercomment         'jo228 orange plate'
_shelx_estimated_absorpt_t_max   0.706
_shelx_estimated_absorpt_t_min   0.706
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.981(4)
 0.019(4)
2. 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
3. Restrained distances
 C5-C16A \\sim C5-C16B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10
\\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16A \\sim C17A \\sim
C18A \\sim C19A \\sim C16B \\sim C17B \\sim C18B \\sim C19B \\sim C20 \\sim C21
\\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29
\\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45
\\sim C46: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C16A) = Uanis(C16B)
5. Rigid body (RIGU) restrains
 C16A, C17A, C18A, C19A, C16B, C17B, C18B, C19B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C21, C22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C16A, C18A, C19A, C17A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C16A, C17A, C18A, C19A}
{C16B, C18B, C19B, C17B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C16B, C17B, C18B, C19B}
{C20, C22, C23, C21} sigma for 1-2: 0.02, 1-3: 0.04
as
{C20, C21, C22, C23}
7. Others
 Sof(C16B)=Sof(C17B)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18B)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(C16A)=Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18A)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C40(H40A,H40B)
8.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C42(H42), C43(H43), C44(H44), C45(H45),
 C46(H46)
8.c Idealised Me refined as rotating group:
 C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C17B(H17D,
 H17E,H17F), C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.249
_oxdiff_exptl_absorpt_empirical_full_min 0.815
_shelx_res_checksum              39363
_cell_oxdiff_length_a            23.6256(4)
_cell_oxdiff_length_b            23.6266(4)
_cell_oxdiff_length_c            15.3117(2)
_cell_oxdiff_angle_alpha         89.9750(13)
_cell_oxdiff_angle_beta          89.9974(13)
_cell_oxdiff_angle_gamma         89.9835(13)
_cell_oxdiff_volume              8546.9(2)
_cell_oxdiff_measurement_reflns_used 40540