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_7718202
_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, C16 H33 Br Fe N Si2'
_chemical_formula_sum            'C47 H68 Br Fe2 N3 Si2'
_chemical_formula_weight         922.83
_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   mixed
_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                111.389(4)
_cell_angle_beta                 90.280(5)
_cell_angle_gamma                107.295(5)
_cell_formula_units_Z            4
_cell_length_a                   16.6856(11)
_cell_length_b                   17.8813(10)
_cell_length_c                   17.8666(11)
_cell_measurement_reflns_used    27363
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.88
_cell_measurement_theta_min      2.07
_cell_volume                     4700.5(5)
_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(2)
_diffrn_detector                 Pilatus200K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 200K'
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
 377 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  0.0584
_diffrn_reflns_av_unetI/netI     0.0952
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34991
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_min         2.072
_diffrn_source                   'Mo Genix'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.552
_exptl_absorpt_correction_T_max  0.7863
_exptl_absorpt_correction_T_min  0.3479
_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    1.304
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.654
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1079
_refine_ls_number_reflns         20059
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.1085
_refine_ls_R_factor_gt           0.0576
_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^)+(0.0750P)^2^+0.4610P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1245
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12721
_reflns_number_total             20059
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           sv1066
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_database_code               7718202
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.679
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C59-C60 \\sim C59-C60A
 with sigma of 0.02
 C60-C61 \\sim C60A-C61A
 with sigma of 0.02
 C60-C65 \\sim C60A-C65A
 with sigma of 0.02
 C59-C61 \\sim C59-C61A
 with sigma of 0.04
 C59-C65 \\sim C59-C65A
 with sigma of 0.04
 C61-C63 \\sim C61A-C63A
 with sigma of 0.04
 C61-C65 \\sim C61A-C65A
 with sigma of 0.04
 C63-C65 \\sim C63A-C65A
 with sigma of 0.04
 C63-C67 \\sim C63A-C67A
 with sigma of 0.02
 C61-C66 \\sim C61A-C66A
 with sigma of 0.02
 C60-C66 \\sim C60A-C66A
 with sigma of 0.04
 C61-C62 \\sim C61A-C62A
 with sigma of 0.02
 C62-C63 \\sim C62A-C63A
 with sigma of 0.02
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C62-C67 \\sim C62A-C67A
 with sigma of 0.04
 C62-C66 \\sim C62A-C66A
 with sigma of 0.04
 C65-C68 \\sim C65A-C68A
 with sigma of 0.02
 C60-C68 \\sim C60A-C68A
 with sigma of 0.04
 C62-H62 \\sim C62A-H62A
 with sigma of 0.02
 C61-H62 \\sim C61A-H62A
 with sigma of 0.04
 H62-C63 \\sim H62A-C63A
 with sigma of 0.04
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 C64-C65 \\sim C64A-C65A
 with sigma of 0.02
 C60-C64 \\sim C60A-C64A
 with sigma of 0.04
 C64-C67 \\sim C64A-C67A
 with sigma of 0.04
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C64-C68 \\sim C64A-C68A
 with sigma of 0.04
 C64-H64 \\sim C64A-H64A
 with sigma of 0.02
 C63-H64 \\sim C63A-H64A
 with sigma of 0.04
 H64-C65 \\sim H64A-C65A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C61) = Uanis(C61A) = Uanis(C66) = Uanis(C66A) = Uanis(C60) = Uanis(C60A)
4. Rigid body (RIGU) restrains
 C63A, C64A, C67A, C62A, C61A, C60A, C65A, C68A, C66A, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.0001
 C60, C65, C68, C64, C63, C67, C62, C61, C66, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.0001
5. Others
 Sof(H59C)=Sof(H59D)=Sof(C60A)=Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=
 Sof(C61A)=Sof(C62A)=Sof(C63A)=Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=
 Sof(C64A)=Sof(C65A)=Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(H62A)=
 Sof(H64A)=1-FVAR(1)
 Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(C64)=
 Sof(H64)=Sof(C65)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(H67C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C59(H59C,H59D), C69(H69A,H69B), C12(H12A,H12B), C22(H22A,H22B)
6.b Me refined with riding coordinates:
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C40(H40A,H40B,
 H40C), C66A(H66D,H66E,H66F), C67A(H67D,H67E,H67F), C68A(H68D,H68E,H68F)
6.c Aromatic/amide H refined with riding coordinates:
 C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C55(H55), C56(H56),
 C57(H57), C58(H58), C62(H62), C64(H64), C72(H72), C74(H74), 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)
6.d Idealised Me refined as rotating group:
 C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), 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), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C),
 C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,
 H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,
 H94B,H94C)
;
_shelx_res_checksum              41373
_shelx_hkl_checksum              21243
_olex2_submission_special_instructions 'No special instructions were received'