Testing the Push-Pull Hypothesis: Lewis Acid Augmented N<sub>2</sub> Activation at Iron.
Geri, Jacob B.; Shanahan, James P.; Szymczak, Nathaniel K.; Journal of the American Chemical Society 139 (2017) 5952–5956; doi:10.1021/jacs.7b01982

data_4131255
_publ_section_title
;
 Testing the Push-Pull Hypothesis: Lewis Acid Augmented N<sub>2</sub>
 Activation at Iron.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5952
_journal_page_last               5956
_journal_paper_doi               10.1021/jacs.7b01982
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety
'C38 H49 B F15 Fe N2 P4, C32 H12 B F24, C6 H5 F'
_chemical_formula_sum            'C76 H66 B2 F40 Fe N2 P4'
_chemical_formula_weight         1968.65
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.29580(9)
_cell_length_b                   12.25554(4)
_cell_length_c                   27.26129(10)
_cell_measurement_reflns_used    84230
_cell_measurement_temperature    80
_cell_measurement_theta_max      69.0460
_cell_measurement_theta_min      2.4330
_cell_volume                     8117.27(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      80
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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   -110.00  70.00   1.00    1.00    --  -20.00   0.00-180.00  180
  2  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  3  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  4  \w    -25.00  43.00   1.00    1.00    --  -20.00  36.00 120.00   68
  5  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00-180.00   45
  6  \w   -173.00-128.00   1.00    4.00    --  -92.00 -36.00 120.00   45
  7  \w   -133.00 -88.00   1.00    4.00    --  -92.00 -36.00 -60.00   45
  8  \w   -104.00 -59.00   1.00    4.00    --  -92.00  36.00  60.00   45
  9  \w   -122.00 -77.00   1.00    4.00    --  -92.00 -72.00  60.00   45
 10  \w   -174.00 -78.00   1.00    4.00    --  -92.00 -72.00-120.00   96
 11  \w    -93.00 -35.00   1.00    4.00    --  -92.00  36.00-120.00   58
 12  \w   -176.00 -77.00   1.00    4.00    --  -92.00 -72.00 -60.00   99
 13  \w   -147.00 -75.00   1.00    4.00    --  -92.00 -72.00-180.00   72
 14  \w   -176.00 -77.00   1.00    4.00    --  -92.00 -72.00 120.00   99
 15  \w   -177.00-116.00   1.00    4.00    --  -92.00 -36.00  60.00   61
 16  \w    -87.00  -9.00   1.00    4.00    --  -92.00  36.00 -60.00   78
 17  \w   -102.00 -14.00   1.00    4.00    --  -92.00  36.00   0.00   88
 18  \w   -102.00 -21.00   1.00    4.00    --  -92.00  72.00 120.00   81
 19  \w   -175.00-104.00   1.00    4.00    --  -92.00 -36.00   0.00   71
 20  \w   -104.00 -52.00   1.00    4.00    --  -92.00  72.00  60.00   52
 21  \w   -109.00 -14.00   1.00    4.00    --  -92.00  72.00-120.00   95
 22  \w   -105.00 -24.00   1.00    4.00    --  -92.00  36.00-120.00   81
 23  \w   -105.00  -2.00   1.00    4.00    --  -92.00  36.00-180.00  103
 24  \w   -106.00  -2.00   1.00    4.00    --  -92.00  72.00 -60.00  104
 25  \w   -106.00  -2.00   1.00    4.00    --  -92.00  72.00 -60.00  104
 26  \w   -107.00 -29.00   1.00    4.00    --  -92.00  72.00   0.00   78
 27  \w   -117.00 -72.00   1.00    4.00    --  -92.00  72.00 180.00   45
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0598330000
_diffrn_orient_matrix_UB_12      -0.0113434000
_diffrn_orient_matrix_UB_13      0.0180276000
_diffrn_orient_matrix_UB_21      0.0080412000
_diffrn_orient_matrix_UB_22      -0.0994679000
_diffrn_orient_matrix_UB_23      -0.0338079000
_diffrn_orient_matrix_UB_31      0.0194056000
_diffrn_orient_matrix_UB_32      0.0760029000
_diffrn_orient_matrix_UB_33      -0.0415397000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0753
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            121702
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.247
_diffrn_reflns_theta_min         3.242
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.486
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82524
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.611
_exptl_crystal_description       block
_exptl_crystal_F_000             3968
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.733
_refine_diff_density_min         -0.685
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 6773 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(4)
_refine_ls_extinction_coef       0.00181(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1458
_refine_ls_number_reflns         14652
_refine_ls_number_restraints     425
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0753
_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^)+(0.0997P)^2^+17.5163P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1947
_refine_ls_wR_factor_ref         0.1949
_reflns_Friedel_coverage         0.893
_reflns_Friedel_fraction_full    0.942
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                14598
_reflns_number_total             14652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b01982_si_002.cif
_cod_data_source_block           3
_cod_database_code               4131255
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C70H61B2F39N2P4Fe
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H7AC,H7AD,H7AA,H7AB} of C7AA, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H8AD,H8AE,H8AF,H1} of C8AB
2. Restrained distances
 F02{-F7A \\sim F7A-F0 \\sim F0-F02{ \\sim F7-F015 \\sim F015-F02Z \\sim F02Z-F7
 with sigma of 0.005
 C02Q-F02{ \\sim C02Q-F7A \\sim C02Q-F0 \\sim C02Q-F7 \\sim C02Q-F015 \\sim
C02Q-F02Z
 with sigma of 0.005
 C02K-F02H \\sim C02K-F025 \\sim C02K-F02U \\sim C02K-F02V \\sim C02K-F4 \\sim
C02K-F02I
 with sigma of 0.005
 F02H-F025 \\sim F025-F02U \\sim F02U-F02H \\sim F02V-F4 \\sim F4-F02I \\sim
F02I-F02V
 with sigma of 0.005
 C7AA-C8AA \\sim C7AA-C8AB
 with sigma of 0.005
 C4AA-C8BA \\sim C12-C0AA
 with sigma of 0.02
 C02J-F2 \\sim C02J-F3 \\sim C02J-F1 \\sim C02J-F2A \\sim C02J-F3A \\sim
C02J-F1A
 with sigma of 0.005
 F2-F3 \\sim F3-F1 \\sim F1-F2 \\sim F2A-F3A \\sim F3A-F1A \\sim F1A-F2A
 with sigma of 0.005
 C02G-F01M \\sim C02G-F01P \\sim C02G-F01N \\sim C02G-F01O \\sim C02G-F01Q
\\sim C02G-F1AA
 with sigma of 0.005
 F01M-F01P \\sim F01P-F01N \\sim F01N-F01M \\sim F01O-F01Q \\sim F01Q-F1AA
\\sim F1AA-F01O
 with sigma of 0.005
 P1-C8AB \\sim P1-C8AA
 with sigma of 0.02
3. Rigid bond restraints
 P1, C7AA, C8AA
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 F0AB, C4A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 2
 C6, C29
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9AA, C18
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F1, F1A, F3, C02J
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F02H, F4, C02K
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F1AA, F01M, F01O, F01P, F01Q, C02G
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F0, F02{, F015, C02Q
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F011, C02O
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C02O, C023
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 P005, C22
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C0AA \\sim C8BA: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.002
C1AA \\sim C5BA: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C7AA \\sim C8AA \\sim C8AB: within 2A with sigma of 0.003 and sigma for
terminal atoms of 0.003
C1AA \\sim C2AA: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C2BA \\sim C3BA: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C2 \\sim C11: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
P005 \\sim C0BA \\sim C49: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
P2 \\sim C4AA \\sim C8BA: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C3 \\sim C15: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C0BA \\sim C49: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(F7A) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F02Z) \\sim Ueq, Uanis(F02{)
\\sim Ueq, Uanis(F015) \\sim Ueq, Uanis(F0) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(F025) \\sim Ueq, Uanis(F02U) \\sim Ueq, Uanis(F02I) \\sim Ueq,
Uanis(F02H) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F02V) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(F3A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F1)
\\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(F01O) \\sim Ueq, Uanis(F01M) \\sim Ueq, Uanis(F1AA) \\sim Ueq,
Uanis(F01P) \\sim Ueq, Uanis(F01Q) \\sim Ueq, Uanis(F01N) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(F02{) = Uanis(F7)
Uanis(F0AB) = Uanis(F0AA)
Uanis(C4) = Uanis(C4A) = Uanis(C5AA) = Uanis(C5AB)
Uanis(C7BA) = Uanis(C7BB) = Uanis(C1) = Uanis(C1A)
Uanis(C5) = Uanis(C5A) = Uanis(C6AA) = Uanis(C6AB)
Uanis(C49) = Uanis(C3)
Uanis(C15) = Uanis(C0BA)
Uanis(C18) = Uanis(C2)
Uanis(C6BA) = Uanis(C1AA)
5. Same fragment restrains
{P2, P002, C37, C19} sigma for 1-2: 0.02, 1-3: 0.02
as
{P0, P003, C32, C43}
{F0AB, C7BB, C4A, C1A, C5AB, C6AB, C5A} sigma for 1-2: 0.02, 1-3: 0.02
{F0AA, C5, C4, C6AA, C5AA, C1, C7BA} sigma for 1-2: 0.02, 1-3: 0.02
as
{F007, C01F, C01I, C02A, C02C, C010, C021}
6. Others
 Sof(F0)=Sof(F02{)=Sof(F7A)=1-FVAR(1)
 Sof(F02Z)=Sof(F7)=Sof(F015)=FVAR(1)
 Sof(F02I)=Sof(F02V)=Sof(F4)=1-FVAR(2)
 Sof(F02H)=Sof(F02U)=Sof(F025)=FVAR(2)
 Sof(F0AB)=Sof(C7BB)=Sof(H7BB)=Sof(C4A)=Sof(C1A)=Sof(H1AD)=Sof(C5AB)=Sof(H5AB)=
 Sof(C6AB)=Sof(H6AB)=Sof(C5A)=Sof(H5A)=1-FVAR(3)
 Sof(F0AA)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(C6AA)=Sof(H6AA)=Sof(C5AA)=Sof(H5AA)=
 Sof(C1)=Sof(H1A)=Sof(C7BA)=Sof(H7BA)=FVAR(3)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(4)
 Sof(F1AA)=Sof(F01O)=Sof(F01Q)=1-FVAR(5)
 Sof(F01M)=Sof(F01N)=Sof(F01P)=FVAR(5)
 Fixed Sof: P0(0.44805) P003(0.44805) C32(0.44805) H32A(0.44805) H32B(0.44805)
 C43(0.44805) H43A(0.44805) H43B(0.44805) P1(0.55195) P2(0.44805) P002(0.44805)
 C37(0.44805) H37A(0.44805) H37B(0.44805) C19(0.44805) H19A(0.44805)
 H19B(0.44805) P3(0.55195) P004(0.55195) P005(0.55195) C0AA(0.55195)
 H0AA(0.55195) H0AB(0.55195) H0AC(0.55195) C0BA(0.55195) H0BA(0.55195)
 H0BB(0.55195) C1AA(0.44805) H1AA(0.44805) H1AB(0.44805) H1AC(0.44805)
 C1BA(0.55195) H1BA(0.55195) H1BB(0.55195) C2(0.44805) H2A(0.44805)
 H2B(0.44805) H2C(0.44805) C2AA(0.44805) H2AA(0.44805) H2AB(0.44805)
 C2BA(0.44805) H2BA(0.44805) H2BB(0.44805) C3(0.44805) H3A(0.44805)
 H3B(0.44805) H3C(0.44805) C3AA(0.44805) H3AA(0.44805) H3AB(0.44805)
 C3BA(0.44805) H3BA(0.44805) H3BB(0.44805) H3BC(0.44805) C4AA(0.44805)
 H4AA(0.44805) H4AB(0.44805) C4BA(0.55195) H4BA(0.55195) H4BB(0.55195)
 H4BC(0.55195) C5BA(0.55195) H5BA(0.55195) H5BB(0.55195) C6(0.55195)
 H6A(0.55195) H6B(0.55195) H6C(0.55195) C6BA(0.55195) H6BA(0.55195)
 H6BB(0.55195) H6BC(0.55195) C7AA(0.55195) H7AC(0.35971) H7AD(0.35971)
 H7AA(0.19224) H7AB(0.19224) C8AA(0.35971) H8AA(0.35971) H8AB(0.35971)
 H8AC(0.35971) C8AB(0.19224) H8AD(0.19224) H8AE(0.19224) H8AF(0.19224)
 C8BA(0.44805) H8BA(0.44805) H8BB(0.44805) H8BC(0.44805) C9(0.55195)
 H9A(0.55195) H9B(0.55195) H9C(0.55195) C9AA(0.55195) H9AA(0.55195)
 H9AB(0.55195) C11(0.44805) H11A(0.44805) H11B(0.44805) C12(0.55195)
 H12A(0.55195) H12B(0.55195) C13(0.55195) H13A(0.55195) H13B(0.55195)
 C14(0.55195) H14A(0.55195) H14B(0.55195) C15(0.44805) H15A(0.44805)
 H15B(0.44805) C16(0.44805) H16A(0.44805) H16B(0.44805) H16C(0.44805)
 C18(0.55195) H18A(0.55195) H18B(0.55195) H18C(0.55195) C22(0.55195)
 H22A(0.55195) H22B(0.55195) C25(0.44805) H25A(0.44805) H25B(0.44805)
 C28(0.44805) H28A(0.44805) H28B(0.44805) H28C(0.44805) C29(0.55195)
 H29A(0.55195) H29B(0.55195) C30(0.55195) H30A(0.55195) H30B(0.55195)
 C31(0.55195) H31A(0.55195) H31B(0.55195) C35(0.44805) H35A(0.44805)
 H35B(0.44805) H35C(0.44805) C40(0.44805) H40A(0.44805) H40B(0.44805)
 C49(0.55195) H49A(0.55195) H49B(0.55195) H49C(0.55195)
7.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C43(H43A,H43B), C37(H37A,H37B), C19(H19A,H19B), C0BA(H0BA,
 H0BB), C1BA(H1BA,H1BB), C2AA(H2AA,H2AB), C2BA(H2BA,H2BB), C3AA(H3AA,H3AB),
 C4AA(H4AA,H4AB), C5BA(H5BA,H5BB), C7AA(H7AC,H7AD), C7AA(H7AA,H7AB), C9AA(H9AA,
 H9AB), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C22(H22A,H22B), C25(H25A,H25B), C29(H29A,H29B), C30(H30A,H30B),
  C31(H31A,H31B), C40(H40A,H40B)
7.b Aromatic/amide H refined with riding coordinates:
 C00X(H00X), C01A(H01A), C01C(H01C), C01D(H01D), C01J(H01J), C01L(H01L),
 C02B(H02B), C013(H013), C016(H016), C018(H018), C020(H020), C022(H022), C5(H5),
  C6AA(H6AA), C5AA(H5AA), C1(H1A), C7BA(H7BA), C7BB(H7BB), C1A(H1AD),
 C5AB(H5AB), C6AB(H6AB), C5A(H5A)
7.c Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C1AA(H1AA,H1AB,H1AC), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C),
 C3BA(H3BA,H3BB,H3BC), C4BA(H4BA,H4BB,H4BC), C6(H6A,H6B,H6C), C6BA(H6BA,H6BB,
 H6BC), C8AA(H8AA,H8AB,H8AC), C8AB(H8AD,H8AE,H8AF), C8BA(H8BA,H8BB,H8BC),
 C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C28(H28A,H28B,H28C),
  C35(H35A,H35B,H35C), C49(H49A,H49B,H49C)
;
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.390
_oxdiff_exptl_absorpt_empirical_full_min 0.714