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_7718200
_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         'C19 H25 Fe I N2'
_chemical_formula_sum            'C19 H25 Fe I N2'
_chemical_formula_weight         464.16
_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             2024-11-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-26 deposited with the CCDC.	2025-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                67.201(5)
_cell_angle_beta                 72.354(6)
_cell_angle_gamma                70.236(5)
_cell_formula_units_Z            10
_cell_length_a                   14.1651(10)
_cell_length_b                   17.6905(12)
_cell_length_c                   22.2919(16)
_cell_measurement_reflns_used    44675
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.36
_cell_measurement_theta_min      1.29
_cell_volume                     4750.0(6)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area WinXpose 2.0.22.0 (STOE, 2016)
;
_computing_data_reduction
;
X-Area Integrate 2.5.1.0 (STOE, 2021)
X-Area LANA 2.6.2.0 (STOE, 2021)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.0, Darmstadt 2021
;
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'imaging plate area detector'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_details
;
 221 frames, detector distance = 130 mm
;
_diffrn_measurement_device       '4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADI VARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2, 0.6 mm diameter, multiple pinhole'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0447
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            34029
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.016
_diffrn_reflns_theta_min         1.290
_diffrn_source                   'Genix Mo HF'
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.420
_exptl_absorpt_correction_T_max  0.8569
_exptl_absorpt_correction_T_min  0.6930
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.623
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2320
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.799
_refine_diff_density_min         -4.661
_refine_diff_density_rms         0.255
_refine_ls_extinction_coef       0.00014(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1047
_refine_ls_number_reflns         17998
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.172
_refine_ls_R_factor_all          0.1111
_refine_ls_R_factor_gt           0.0689
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+112.2138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1398
_refine_ls_wR_factor_ref         0.1747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12676
_reflns_number_total             17998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           i3394
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_database_code               7718200
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.656
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Fe4) = Uanis(C69A) = Uanis(C69) = Uanis(C70A) = Uanis(C70) = Uanis(C71A)
= Uanis(C71) = Uanis(C67A) = Uanis(C67) = Uanis(C68) = Uanis(C68A) =
Uanis(C74A) = Uanis(C74) = Uanis(C75A) = Uanis(C75) = Uanis(C76A) = Uanis(C76)
= Uanis(C72A) = Uanis(C72) = Uanis(C73A) = Uanis(C73)
3. Rigid body (RIGU) restrains
 C60, C61, C62, C63, C64, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C33, C29, C30, C31
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: C67A(0.5) C67(0.5) C68(0.5) C68A(0.5) C69A(0.5) C69(0.5) C70A(0.5)
 C70(0.5) C71(0.5) C71A(0.5) C72(0.5) H72A(0.5) H72B(0.5) H72C(0.5) C72A(0.5)
 H72D(0.5) H72E(0.5) H72F(0.5) C73(0.5) H73A(0.5) H73B(0.5) H73C(0.5) C73A(0.5)
 H73D(0.5) H73E(0.5) H73F(0.5) C74A(0.5) H74A(0.5) H74B(0.5) H74C(0.5) C74(0.5)
 H74D(0.5) H74E(0.5) H74F(0.5) C75A(0.5) H75A(0.5) H75B(0.5) H75C(0.5) C75(0.5)
 H75D(0.5) H75E(0.5) H75F(0.5) C76A(0.5) H76A(0.5) H76B(0.5) H76C(0.5) C76(0.5)
 H76D(0.5) H76E(0.5) H76F(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C61(H61), C62(H62), C63(H63), C64(H64), C80(H80), C81(H81), C82(H82),
 C83(H83), C4(H4), C5(H5), C6(H6), C7(H7), C42(H42), C43(H43), C44(H44),
 C45(H45), C23(H23), C24(H24), C25(H25), C26(H26)
5.b Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C72(H72A,H72B,H72C), C72A(H72D,H72E,
 H72F), C73(H73A,H73B,H73C), C73A(H73D,H73E,H73F), C74A(H74A,H74B,H74C),
 C74(H74D,H74E,H74F), C75A(H75A,H75B,H75C), C75(H75D,H75E,H75F), C76A(H76A,H76B,
 H76C), C76(H76D,H76E,H76F), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C91(H91A,
 H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C),
 C95(H95A,H95B,H95C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C53(H53A,H53B,H53C), C54(H54A,
 H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C),
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C)
;
_shelx_res_checksum              7233
_shelx_hkl_checksum              64069
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '130.0 mm'
_stoe_detector_pixelsize_x       '0.150 mm'
_stoe_detector_pixelsize_y       '0.150 mm'
_stoe_detector_size_x            '34.0 cm'
_stoe_detector_size_y            '34.0 cm'
_stoe_evaluation_integration_a   20.0
_stoe_evaluation_integration_b   8.0
_stoe_evaluation_integration_ems 0.020
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max -
_stoe_evaluation_lana_bos_l_odd_max -
_stoe_evaluation_lana_completeness 95.9
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order 1
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 52.0
_stoe_evaluation_lana_max_2theta_desired 52.0
_stoe_evaluation_lana_mean_redundancy 1.9
_stoe_evaluation_lana_number_refls_after_or 34063
_stoe_evaluation_lana_number_refls_outliers 4313
_stoe_evaluation_lana_number_refls_total 38376
_stoe_evaluation_lana_number_refls_unique 18017
_stoe_evaluation_lana_number_refls_written 34063
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group -1
_stoe_evaluation_lana_table
;
2Theta           4.9   10.5   16.1   21.7   27.3   32.9   38.5   44.1   49.7
<Resolution>    6.84   3.70   2.48   1.87   1.50   1.25   1.07   0.94   0.85
N(total)         137    582   1404   2531   3883   5472   7101   8925   8341
<Redundancy>     2.0    1.9    2.0    2.0    2.0    1.9    1.9    1.9    1.8
Complet. [%%]    88.2   91.8   95.9   99.0   98.9   99.2   98.9   98.7   88.1
<I/sigma>      147.6  148.8  178.9  158.4  100.7   65.5   40.6   20.8   10.7
R(int)         0.070  0.059  0.032  0.030  0.031  0.039  0.048  0.069  0.103
;
_stoe_measurement_identifier     i3394
_stoe_measurement_max_exposure_per_frame '120.0 s'
_stoe_measurement_mean_exposure_per_frame '120.0 s'
_stoe_measurement_min_exposure_per_frame '120.0 s'
_stoe_measurement_total_exposure_time '7.4 h'
_stoe_measurement_total_frame_number 221
_stoe_measurement_total_run_number 3
_stoe_measurement_tube_power     '50.0 W'