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_7125833
_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         'C18 H54 Fe N3 Si6, 2(C10 H22 K0.5 O4)'
_chemical_formula_sum            'C38 H98 Fe K N3 O8 Si6'
_chemical_formula_weight         988.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 92.3350(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4864(6)
_cell_length_b                   17.4686(7)
_cell_length_c                   21.7327(9)
_cell_measurement_reflns_used    9735
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      27.5041
_cell_measurement_theta_min      2.5135
_cell_volume                     5874.4(4)
_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 SMART APEX2 area detector'
_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  0.0512
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            160701
_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         27.571
_diffrn_reflns_theta_min         2.209
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.491
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D., J. Appl. Cryst. 48 (2015) 3-10'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.118
_exptl_crystal_description       block
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.556
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         13562
_refine_ls_number_restraints     164
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0372P)^2^+3.9788P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0839
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10742
_reflns_number_total             13562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08968c2.cif
_cod_data_source_block           k18c6_fehmds3
_cod_depositor_comments
'Adding full bibliography for 7125833--7125836.cif.'
_cod_database_code               7125833
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.839
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1L-C1L = O1L-C3L = O1LA-C1LA = O1LA-C3LA
 1.45 with sigma of 0.01
 C1L-C2L = C3L-C4L = C1LA-C2LA = C3LA-C4LA
 1.54 with sigma of 0.01
 O1L-C2L \\sim O1L-C4L \\sim O1LA-C2LA \\sim O1LA-C4LA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1L \\sim C1L \\sim C2L \\sim C3L \\sim C4L \\sim O1LA \\sim C1LA \\sim C2LA
\\sim C3LA \\sim C4LA: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(O1L) \\sim Ueq, Uanis(C1L) \\sim Ueq, Uanis(C2L) \\sim Ueq, Uanis(C3L)
\\sim Ueq, Uanis(C4L) \\sim Ueq, Uanis(O1LA) \\sim Ueq, Uanis(C1LA) \\sim Ueq,
Uanis(C2LA) \\sim Ueq, Uanis(C3LA) \\sim Ueq, Uanis(C4LA) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(K1) = Uanis(K1A)
4. Rigid body (RIGU) restrains
 O1L, C1L, C2L, C3L, C4L, O1LA, C1LA, C2LA, C3LA, C4LA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: K1(0.25) K1A(0.25) O1L(0.35) C1L(0.35) H1LA(0.35) H1LB(0.35)
 C2L(0.35) H2LA(0.35) H2LB(0.35) H2LC(0.35) C3L(0.35) H3LA(0.35) H3LB(0.35)
 C4L(0.35) H4LA(0.35) H4LB(0.35) H4LC(0.35) O1LA(0.65) C1LA(0.65) H1LC(0.65)
 H1LD(0.65) C2LA(0.65) H2LD(0.65) H2LE(0.65) H2LF(0.65) C3LA(0.65) H3LC(0.65)
 H3LD(0.65) C4LA(0.65) H4LD(0.65) H4LE(0.65) H4LF(0.65)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B),
 C2'(H2'A,H2'B), C3'(H3'A,H3'B), C5'(H5'A,H5'B), C6'(H6'A,H6'B), C8'(H8'A,H8'B),
  C9'(H9'A,H9'B), C1L(H1LA,H1LB), C3L(H3LA,H3LB), C1LA(H1LC,H1LD), C3LA(H3LC,
 H3LD), C1L'(H1LE,H1LF), C3L'(H3LE,H3LF)
6.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C2L(H2LA,
 H2LB,H2LC), C4L(H4LA,H4LB,H4LC), C2LA(H2LD,H2LE,H2LF), C4LA(H4LD,H4LE,H4LF),
 C2L'(H2LG,H2LH,H2LI), C4L'(H4LG,H4LH,H4LI)
;
_shelx_res_checksum              30311
_olex2_submission_special_instructions 'No special instructions were received'