A Tertiary Carbon‒Iron Bond as an FeICl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron
Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.; Organometallics 35 (2016) 1643–; doi:10.1021/acs.organomet.6b00108

data_4088452
_publ_section_title
;
 A Tertiary Carbon--Iron Bond as an FeICl Synthon and the Reductive
 Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to
 Low-Valent Iron
;
_journal_issue                   11
_journal_name_full               Organometallics
_journal_page_first              1643
_journal_paper_doi               10.1021/acs.organomet.6b00108
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C24.57 H61.63 Fe2 N2 P8'
_chemical_formula_sum            'C24.566 H61.633 Fe2 N2 P8'
_chemical_formula_weight         744.69
_chemical_name_systematic
'bis(dimethylphosphinomethane)iron dinitrogen dimer'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_audit_creation_date             2016-01-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90.684(2)
_cell_angle_beta                 90.764(3)
_cell_angle_gamma                115.560(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2918(13)
_cell_length_b                   9.6140(13)
_cell_length_c                   23.399(3)
_cell_measurement_reflns_used    9074
_cell_measurement_temperature    105
_cell_measurement_theta_max      28.48
_cell_measurement_theta_min      2.56
_cell_volume                     1885.2(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2013)'
_diffrn_ambient_temperature      105.29
_diffrn_measured_fraction_theta_full 0.9879
_diffrn_measured_fraction_theta_max 0.9844
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            27161
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         28.49
_diffrn_reflns_theta_min         2.43
_exptl_absorpt_coefficient_mu    1.127
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6277
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'SADABS-2014/3 - Bruker AXS area detector scaling and absorption correction'
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.3118
_exptl_crystal_description       plate
_exptl_crystal_F_000             793.2593
_exptl_crystal_preparation       'Saturated hexane solution held at -30 C.'
_exptl_crystal_recrystallization_method
'Saturated N-hexane solution held at -35 C.'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.6171
_refine_diff_density_min         -1.2833
_refine_diff_density_rms         0.2959
_refine_ls_d_res_high            0.7450
_refine_ls_d_res_low             8.3807
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   0.9984
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    138
_refine_ls_number_parameters     458
_refine_ls_number_reflns         9416
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      0.9967
_refine_ls_R_factor_all          0.1052
_refine_ls_R_factor_gt           0.0996
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0681P)^2^+54.3988P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2696
_refine_ls_wR_factor_ref         0.2798
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -12
_reflns_limit_k_max              12
_reflns_limit_k_min              -12
_reflns_limit_l_max              31
_reflns_limit_l_min              0
_reflns_number_gt                8694
_reflns_number_total             9416
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            om6b00108_si_002.cif
_cod_data_source_block           DMPEFeN2
_cod_original_cell_volume        1885.2(5)
_cod_database_code               4088452
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H3aa,H3ab,H3b} of C3, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, {H5a,H5b,H5c} of C5, {H12a,H12b,H12c} of C12,
  {H2a,H2b,H2c} of C2, {H14e,H14f,H14g} of C14', {H11a,H11b,H11c} of C11, {H6'a,
  H6'b,H6'c} of C6', {H23g,H23h,H23i} of C23', {H8a,H8b,H8c} of C8, {H15a,H15b,
  H15c} of C15, {H1a,H1b,H1c} of C1, {H6a,H6b,H6c} of C6, {H7a,H7b,H7c} of C7,
  {H5'a,H5'b,H5'c} of C5', {H13a,H13b,H13c} of C13, {H13d,H13e,H13f} of C13'
2. Rigid bond restraints
 C23', C24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C22 \\sim C21: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C24 \\sim C25: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(H17d)=Sof(H17e)=Sof(H17f)=Sof(H18d)=Sof(H18e)=Sof(H18f)=Sof(H19d)=
 Sof(H19e)=Sof(H19f)=Sof(H20d)=Sof(H20e)=Sof(H20f)=Sof(H23d)=Sof(H23e)=
 Sof(H23f)=Sof(C5)=Sof(H5a)=Sof(H5b)=Sof(H5c)=Sof(C4')=Sof(H4'a)=Sof(H4'b)=
 Sof(C6')=Sof(H6'a)=Sof(H6'b)=Sof(H6'c)=Sof(C13')=Sof(H13d)=Sof(H13e)=Sof(H13f)=
 Sof(C14')=Sof(H14e)=Sof(H14f)=Sof(H14g)=Sof(C15')=Sof(H15d)=Sof(H15e)=Sof(P6B)=
 Sof(P8B)=Sof(P5B)=Sof(P7B)=Sof(H3b)=1-FVAR(1)
 Sof(H17a)=Sof(H17b)=Sof(H17c)=Sof(H18a)=Sof(H18b)=Sof(H18c)=Sof(H19a)=
 Sof(H19b)=Sof(H19c)=Sof(H20a)=Sof(H20b)=Sof(H20c)=Sof(H22a)=Sof(C26)=Sof(H22c)=
 Sof(H23a)=Sof(H23b)=Sof(H23c)=Sof(C4)=Sof(H4a)=Sof(H4b)=Sof(C6)=Sof(H6a)=
 Sof(H6b)=Sof(H6c)=Sof(C13)=Sof(H13a)=Sof(H13b)=Sof(H13c)=Sof(C14)=Sof(H14a)=
 Sof(H14b)=Sof(C14B)=Sof(H14c)=Sof(H14d)=Sof(C25)=Sof(H25a)=Sof(H25b)=Sof(C5')=
 Sof(H5'a)=Sof(H5'b)=Sof(H5'c)=Sof(P5)=Sof(P8)=Sof(P7)=Sof(P6)=Sof(H3aa)=
 Sof(H3ab)=FVAR(1)
 Fixed Sof: C15(0.5) H15a(0.5) H15b(0.5) H15c(0.5) C24(0.5) C16'(0.5)
 H16a(0.5) H16b(0.5) C23'(0.5) H23g(0.5) H23h(0.5) H23i(0.5) H24(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C9(H9a,H9b), C10(H10a,H10b), C4(H4a,H4b), C14(H14a,H14b), C14B(H14c,H14d),
 C25(H25a,H25b), C4'(H4'a,H4'b), C15'(H15d,H15e), C16'(H16a,H16b), C21(H21a,
 H21b), C3(H3aa,H3ab)
5.b Me refined with riding coordinates:
 C17(H17a,H17b,H17c), C17(H17d,H17e,H17f), C18(H18a,H18b,H18c), C18(H18d,H18e,
 H18f), C19(H19a,H19b,H19c), C19(H19d,H19e,H19f), C20(H20a,H20b,H20c), C20(H20d,
 H20e,H20f), C23(H23a,H23b,H23c), C23(H23d,H23e,H23f)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3b), C24(H24)
5.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c), C7(H7a,H7b,H7c), C8(H8a,H8b,H8c), C11(H11a,
 H11b,H11c), C12(H12a,H12b,H12c), C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C13(H13a,
 H13b,H13c), C15(H15a,H15b,H15c), C5'(H5'a,H5'b,H5'c), C6'(H6'a,H6'b,H6'c),
 C13'(H13d,H13e,H13f), C14'(H14e,H14f,H14g), C23'(H23g,H23h,H23i)
;
_shelx_res_checksum              58953
_olex2_exptl_crystal_mounting_method 'N-paratone on a nylon loop'
_olex2_submission_original_sample_id amt001100
_olex2_submission_special_instructions 'No special instructions were received'