The “pogo stick” complex [FeCp*{N(SiMe3)2}]: spin state properties, adduct formation with Lewis bases, and reactivity towards weakly Brønsted acidic protonated NHCs
Zinke, Julian; Bruhn, Clemens; Demeshko, Serhiy; Siemeling, Ulrich; Dalton Transactions 54 (2025) 5812–5828; doi:10.1039/D5DT00300H

data_7718192
_publ_section_title
;
 The &#x201C;pogo stick&#x201D; complex [FeCp*{N(SiMe3)2}]: spin state
 properties, adduct formation with Lewis bases, and reactivity towards
 weakly Br\/onsted acidic protonated NHCs
;
_journal_issue                   14
_journal_name_full               'Dalton Transactions'
_journal_page_first              5812
_journal_page_last               5828
_journal_paper_doi               10.1039/D5DT00300H
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C16 H33 Br Fe N Si2, C12 H28 N, 0.5 (C6 H6)'
_chemical_formula_sum            'C31 H64 Br Fe N2 Si2'
_chemical_formula_weight         656.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-05 deposited with the CCDC.	2025-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 141.300(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.820(2)
_cell_length_b                   15.1513(7)
_cell_length_c                   26.4423(16)
_cell_measurement_reflns_used    15779
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.12
_cell_measurement_theta_min      2.05
_cell_volume                     7970.7(9)
_computing_cell_refinement       'X-Area Recipe 1.36.0.0 (STOE, 2020)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.170.0 (STOE, 2020)'
_computing_data_reduction
;
X-Area Integrate 1.78.3.0 (STOE, 2020)
X-Area LANA 1.83.8.0 (STOE, 2020)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
 254 frames, detector distance = 40 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0837
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            19715
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.999
_diffrn_reflns_theta_min         2.233
_diffrn_source                   'Mo Genix'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.460
_exptl_absorpt_correction_T_max  0.8785
_exptl_absorpt_correction_T_min  0.5264
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270. Afterwards scaling of
reflection intensities was performed within STOE LANA. J. Koziskova, F. Hahn,
J. Richter, J. Kozisek, Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136-140.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.095
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2824
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.480
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         9536
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.1075
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0418P)^2^+11.4212P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.1165
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5843
_reflns_number_total             9536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           sv1069a
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_original_cell_volume        7970.8(9)
_cod_database_code               7718192
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.769
_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, All C(H,H,H,H,H,H) groups
2. Others
 Fixed Sof: C17A(0.4) H17A(0.4) H17B(0.4) C17(0.6) H17C(0.6) H17D(0.6)
 C18(0.6) H18A(0.6) H18B(0.6) C18A(0.4) H18C(0.4) H18D(0.4) H19A(0.6) H19B(0.6)
 H19C(0.6) H19D(0.4) H19E(0.4) H19F(0.4) C20A(0.4) H20A(0.4) H20B(0.4) C20(0.6)
 H20C(0.6) H20D(0.6) C21A(0.4) H21A(0.4) H21B(0.4) C21(0.6) H21C(0.6) H21D(0.6)
 H22A(0.6) H22B(0.6) H22C(0.6) H22D(0.4) H22E(0.4) H22F(0.4) C23A(0.4)
 H23A(0.4) H23B(0.4) C23(0.6) H23C(0.6) H23D(0.6) C24A(0.4) H24A(0.4) H24B(0.4)
 C24(0.6) H24C(0.6) H24D(0.6) H25A(0.6) H25B(0.6) H25C(0.6) H25D(0.4) H25E(0.4)
 H25F(0.4) C26A(0.4) H26A(0.4) H26B(0.4) C26(0.6) H26C(0.6) H26D(0.6) C27(0.6)
 H27A(0.6) H27B(0.6) C27A(0.4) H27C(0.4) H27D(0.4) H28A(0.6) H28B(0.6)
 H28C(0.6) H28D(0.4) H28E(0.4) H28F(0.4)
3.a Secondary CH2 refined with riding coordinates:
 C17A(H17A,H17B), C17(H17C,H17D), C18(H18A,H18B), C18A(H18C,H18D), C20A(H20A,
 H20B), C20(H20C,H20D), C21A(H21A,H21B), C21(H21C,H21D), C23A(H23A,H23B),
 C23(H23C,H23D), C24A(H24A,H24B), C24(H24C,H24D), C26A(H26A,H26B), C26(H26C,
 H26D), C27(H27A,H27B), C27A(H27C,H27D)
3.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C30(H30), C31(H31)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C19(H19A,H19B,
 H19C), C19(H19D,H19E,H19F), C22(H22A,H22B,H22C), C22(H22D,H22E,H22F), C25(H25A,
 H25B,H25C), C25(H25D,H25E,H25F), C28(H28A,H28B,H28C), C28(H28D,H28E,H28F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23383
_shelx_hkl_checksum              28571
_shelx_fab_checksum              29242
_olex2_submission_special_instructions 'No special instructions were received'