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_7718196
_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         'C31 H35 Fe N2, C10 H15 Cl2 Fe, 2(C7 H8)'
_chemical_formula_sum            'C55 H66 Cl2 Fe2 N2'
_chemical_formula_weight         937.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                70.092(4)
_cell_angle_beta                 89.668(4)
_cell_angle_gamma                73.820(4)
_cell_formula_units_Z            2
_cell_length_a                   12.5906(7)
_cell_length_b                   14.1602(7)
_cell_length_c                   15.1245(8)
_cell_measurement_reflns_used    14222
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.00
_cell_measurement_theta_min      3.12
_cell_volume                     2423.0(2)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_details
;
 1766 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 mm, 0.6 diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0542
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            22014
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         71.010
_diffrn_reflns_theta_min         3.123
_diffrn_source                   Cu-Genix
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    6.093
_exptl_absorpt_correction_T_max  0.7925
_exptl_absorpt_correction_T_min  0.1804
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.184
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     563
_refine_ls_number_reflns         8991
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0987
_refine_ls_R_factor_gt           0.0631
_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^)+(0.0749P)^2^+3.2500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1413
_refine_ls_wR_factor_ref         0.1593
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6415
_reflns_number_total             8991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           sv1034
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_database_code               7718196
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.446
_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.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C22(H22A,H22B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C15(H15), C17(H17), C25(H25), C27(H27), C50(H50), C51(H51), C52(H52), C53(H53),
  C54(H54), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C55(H55A,H55B,H55C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              85978
_shelx_hkl_checksum              49709
_olex2_submission_special_instructions 'No special instructions were received'