A hampered oxidative addition of pre-coordinated pincer ligands can favour alternative pathways of activation.
Wehmeyer, Frerk-Ulfert; Langer, Robert; Chemical communications (Cambridge, England) 59 (2023) 6004–6007; doi:10.1039/d3cc00874f

data_7131558
_publ_section_title
;
 A hampered oxidative addition of pre-coordinated pincer ligands can
 favour alternative pathways of activation.
;
_journal_issue                   40
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6004
_journal_page_last               6007
_journal_paper_doi               10.1039/d3cc00874f
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C50 H46 B P4 Pt, F6 P, 0.5(C7 H8)'
_chemical_formula_sum            'C53.5 H50 B F6 P5 Pt'
_chemical_formula_weight         1167.68
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-21
_audit_creation_method
; 
Olex2 1.3 
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408) 
;
_audit_update_record
;
2023-02-22 deposited with the CCDC.	2023-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.88(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.728(2)
_cell_length_b                   26.813(5)
_cell_length_c                   17.242(3)
_cell_measurement_reflns_used    625
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.89
_cell_measurement_theta_min      1.48
_cell_volume                     5285.5(17)
_computing_cell_refinement       'X-Area Recipe 1.33.0.0 (STOE & Cie, 2015)'
_computing_data_collection       'X-Area WinXpose 2.0.22.0 (STOE & Cie, 2016)'
_computing_data_reduction        'X-Area 1.90 (STOE & Cie, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      170
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0946
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            44794
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         1.519
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.862
_exptl_absorpt_correction_T_max  0.5953
_exptl_absorpt_correction_T_min  0.2648
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'X-RED32 1.57 (STOE & Cie, 2011)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       needle
_exptl_crystal_F_000             2332
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.070
_refine_diff_density_min         -1.889
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         10384
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0591
_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^)+(0.0365P)^2^+35.0411P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1385
_refine_ls_wR_factor_ref         0.1456
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8814
_reflns_number_total             10384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00874f18.cif
_cod_data_source_block           frerk_xshape
_cod_depositor_comments
'Adding full bibliography for 7131557--7131558.cif.'
_cod_original_cell_volume        5285.5(19)
_cod_original_formula_sum        'C53.50 H50 B F6 P5 Pt'
_cod_database_code               7131558
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.673
_shelx_estimated_absorpt_t_min   0.394
_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. Restrained distances 
 C7S-C1S 
 1.51 with sigma of 0.02 
 C1S-C2S = C1S-C6S = C3S-C4S 
 1.39 with sigma of 0.02 
 C2S-C3S = C4S-C5S = C5S-C6S 
 1.38 with sigma of 0.02 
 C1S-C3S 
 2.42 with sigma of 0.04 
 C2S-C4S 
 2.39 with sigma of 0.04 
 C7S-C2S = C7S-C6S 
 2.52 with sigma of 0.04 
 C1S-C5S 
 2.41 with sigma of 0.04 
 C3S-C5S = C4S-C6S 
 2.4 with sigma of 0.04 
 C1S-C2S \\sim C2S-C3S \\sim C3S-C4S \\sim C4S-C5S \\sim C5S-C6S \\sim C6S-C1S 
 with sigma of 0.02 
 C1S-C5S \\sim C1S-C3S \\sim C6S-C4S \\sim C2S-C6S \\sim C3S-C5S \\sim C2S-C4S 
 with sigma of 0.04 
 C7S-C6S \\sim C7S-C2S 
 with sigma of 0.04 
3. Restrained planarity 
 C7S, C1S, C2S, C3S, C4S, C5S, C6S 
 with sigma of 0.1 
4. Uiso/Uaniso restraints and constraints 
C7S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim C5S \\sim C6S: within 2A with 
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A 
Uanis(C1A) = Uanis(C2A) = Uanis(C3A) = Uanis(C4A) = Uanis(C5A) = Uanis(C6A) 
5. Rigid body (RIGU) restrains 
 C7S, C1S, C2S, C3S, C4S, C5S, C6S 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
6. Others 
 Fixed Sof: C7S(0.5) H7SA(0.5) H7SB(0.5) H7SC(0.5) C1S(0.5) C2S(0.5) H2S(0.5) 
 C3S(0.5) H3S(0.5) C4S(0.5) H4S(0.5) C5S(0.5) H5S(0.5) C6S(0.5) H6S(0.5) 
7.a Secondary CH2 refined with riding coordinates: 
 C2(H2A,H2B), C1(H1A,H1B) 
7.b Aromatic/amide H refined with riding coordinates: 
 C48A(H48A), C45A(H45A), C27A(H27A), C30A(H30A), C44A(H44A), C26A(H26A), 
 C47A(H47A), C46A(H46A), C38A(H38A), C18A(H18A), C29A(H29A), C20A(H20A), 
 C32A(H32A), C36A(H36A), C2A(H2AA), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), 
 C14A(H14A), C33A(H33A), C34A(H34A), C28A(H28A), C16A(H16A), C39A(H39A), 
 C22A(H22A), C12A(H12A), C24A(H24A), C15A(H15A), C17A(H17A), C23A(H23A), 
 C21A(H21A), C42A(H42A), C35A(H35A), C8A(H8A), C11A(H11A), C10A(H10A), C9A(H9A), 
  C40A(H40A), C41A(H41A), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S) 
7.c Fitted hexagon refined as free rotating group: 
 C1A(C2A,C3A,C4A,C5A,C6A) 
7.d Idealised Me refined as rotating group: 
 C7S(H7SA,H7SB,H7SC) 
;
_shelx_res_checksum              85
_shelx_hkl_checksum              88243
_olex2_submission_special_instructions 'No special instructions were received'