The ambiguous behaviour of diphosphines towards the quasilinear iron(i) complex [Fe(N(SiMe<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]<sup>-</sup> - between inertness, P-C bond cleavage and C-C double bond isomerisation.
Werncke, Christian Gunnar; Müller, Igor; Chemical communications (Cambridge, England) 56 (2020) 2268–2271; doi:10.1039/c9cc08968c

data_7125836
_publ_section_title
;
 The ambiguous behaviour of diphosphines towards the quasilinear iron(i)
 complex [Fe(N(SiMe<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]<sup>-</sup> -
 between inertness, P-C bond cleavage and C-C double bond isomerisation.
;
_journal_issue                   15
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2268
_journal_page_last               2271
_journal_paper_doi               10.1039/c9cc08968c
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C38 H58 Fe N2 P2 Si4, C20 H40 K O8'
_chemical_formula_sum            'C58 H98 Fe K N2 O8 P2 Si4'
_chemical_formula_weight         1220.63
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-06
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2019-11-08 deposited with the CCDC.	2020-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.326(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5633(5)
_cell_length_b                   35.5283(14)
_cell_length_c                   15.3551(7)
_cell_measurement_reflns_used    9231
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.94
_cell_measurement_theta_min      2.36
_cell_volume                     6763.2(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Quest D8'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            158557
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.977
_diffrn_reflns_theta_min         2.183
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.451
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7141
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1249 before and 0.0515 after correction. The Ratio of minimum to maximum transmission is 0.9579. The \l/2 correction factor is Not present.'
_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    1.199
_exptl_crystal_description       block
_exptl_crystal_F_000             2620
_exptl_crystal_size_max          0.333
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.104
_refine_diff_density_min         -0.550
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     751
_refine_ls_number_reflns         14674
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0511
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0388P)^2^+8.4157P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12655
_reflns_number_total             14674
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08968c2.cif
_cod_data_source_block           k18c6_fe_hmds2_trans_dppee
_cod_depositor_comments
'Adding full bibliography for 7125833--7125836.cif.'
_cod_database_code               7125836
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.864
_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
 P2-C00U \\sim P2-C26
 with sigma of 0.02
 C00U-C31 \\sim C26-C25
 with sigma of 0.02
 C00U-C27 \\sim C26-C22
 with sigma of 0.02
 C31-C30 \\sim C25-C1AA
 with sigma of 0.02
 C27-C28 \\sim C22-C23
 with sigma of 0.02
 C29-C30 \\sim C24-C1AA
 with sigma of 0.02
 C29-C28 \\sim C24-C23
 with sigma of 0.02
 P2-C31 \\sim P2-C25
 with sigma of 0.04
 P2-C27 \\sim P2-C22
 with sigma of 0.04
 C00U-C30 \\sim C26-C1AA
 with sigma of 0.04
 C00U-C28 \\sim C26-C23
 with sigma of 0.04
 C31-C27 \\sim C25-C22
 with sigma of 0.04
 C31-C29 \\sim C25-C24
 with sigma of 0.04
 C27-C29 \\sim C22-C24
 with sigma of 0.04
 C30-C28 \\sim C1AA-C23
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C22 \\sim C26 \\sim C25 \\sim C1AA \\sim C23 \\sim C24: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C27 \\sim C00U \\sim C31 \\sim C30 \\sim C29 \\sim C28: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C00U) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C22) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C1AA)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C27) \\sim Ueq, Uanis(C00U) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C22, C26, C25, C1AA, C23, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C00U, C31, C30, C29, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C00U(0.8) C31(0.8) H31(0.8) C27(0.8) H27(0.8) C29(0.8) H29(0.8)
 C30(0.8) H30(0.8) C28(0.8) H28(0.8) C26(0.2) C25(0.2) H25(0.2) C1AA(0.2)
 H1AA(0.2) C24(0.2) H24(0.2) C23(0.2) H23(0.2) C22(0.2) H22(0.2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C01D(H01A,H01B), C01H(H01C,H01D), C01I(H01E,H01F), C01J(H01G,H01H), C01L(H01I,
 H01J), C01M(H01K,H01L), C01O(H01M,H01N), C01P(H01O,H01P), C01Q(H01Q,H01R),
 C01S(H01S,H01T), C01U(H01U,H01V), C01V(H01W,H01X), C01X(H01Y,H), C01Y(H01Z,HA),
  C01Z(H01,HB), C020(H02A,H02B), C021(H02C,H02D), C022(H02E,H02F), C023(H02G,
 H02H), C024(H02I,H02J)
6.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C16(H16), C18(H18), C43(H43), C17(H17), C36(H36), C19(H19),
 C20(H20), C40(H40), C31(H31), C42(H42), C32(H32), C41(H41), C35(H35), C27(H27),
  C34(H34), C29(H29), C30(H30), C33(H33), C28(H28), C25(H25), C1AA(H1AA),
 C24(H24), C23(H23), C22(H22)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C),
 C13(H13A,H13B,H13C), C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C14(H14A,H14B,H14C),
  C11(H11A,H11B,H11C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              72707
_olex2_submission_special_instructions 'No special instructions were received'