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_7131557
_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 H45 B Cl P4 Pt, F6 P, C4 H10 O, 0.75(C4 H8 O)'
_chemical_formula_sum            'C57 H61 B Cl F6 O1.75 P5 Pt'
_chemical_formula_weight         1284.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-25
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.859(5)
_cell_length_b                   23.456(5)
_cell_length_c                   20.743(4)
_cell_measurement_reflns_used    29.50
_cell_measurement_temperature    170
_cell_measurement_theta_max      29.50
_cell_measurement_theta_min      1.73
_cell_volume                     11609(4)
_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 2018/2 (Sheldrick, 2018)'
_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 0.999
_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  0.0935
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            69616
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.564
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.660
_exptl_absorpt_correction_T_max  0.9734
_exptl_absorpt_correction_T_min  0.9317
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'X-RED32 1.57 (STOE & Cie, 2011)'
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_description       plate
_exptl_crystal_F_000             5168
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.629
_refine_diff_density_min         -1.052
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     672
_refine_ls_number_reflns         11412
_refine_ls_number_restraints     150
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0510
_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^)+(0.0742P)^2^+0.7214P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1246
_refine_ls_wR_factor_ref         0.1424
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7092
_reflns_number_total             11412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00874f18.cif
_cod_data_source_block           frerk1
_cod_depositor_comments
'Adding full bibliography for 7131557--7131558.cif.'
_cod_database_code               7131557
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.618
_shelx_estimated_absorpt_t_min   0.416
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1S-C2S = C1S-O1S
 1.44 with sigma of 0.02
 C2S-C3S = C4S-O1S
 1.53 with sigma of 0.02
 C3S-C4S
 1.54 with sigma of 0.02
 C7S-C6S
 1.54 with sigma of 0.02
 O2S-C8S = O2S-C5S
 1.44 with sigma of 0.02
 C8S-C7S = C6S-C5S
 1.53 with sigma of 0.02
 C1S-C3S = C1S-C4S = C2S-C4S = C3S-O1S
 2.38 with sigma of 0.04
 O2S-C7S = O2S-C6S = C8S-C6S = C7S-C5S
 2.38 with sigma of 0.04
 C1S-C3S \\sim C1S-C4S
 with sigma of 0.04
 C2S-C3S \\sim C3S-C4S \\sim C4S-O1S
 with sigma of 0.02
 C1S-C2S \\sim C1S-O1S
 with sigma of 0.02
 C3S-O1S \\sim C2S-C4S
 with sigma of 0.04
 O2S-C8S \\sim O2S-C5S
 with sigma of 0.02
 C7S-C5S \\sim C8S-C6S
 with sigma of 0.04
 C8S-C7S \\sim C7S-C6S \\sim C6S-C5S
 with sigma of 0.02
 O2S-C7S \\sim O2S-C6S
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1S \\sim C2S \\sim C3S \\sim C4S \\sim O1S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O2S \\sim C8S \\sim C7S \\sim C6S \\sim C5S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C46A) = Uanis(C47A) = Uanis(C48A) = Uanis(C43A) = Uanis(C44A) =
Uanis(C45A)
4. Rigid body (RIGU) restrains
 C1S, C2S, C3S, C4S, O1S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2S, C8S, C7S, C6S, C5S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C1S(0.5) H1Sa(0.5) H1Sb(0.5) C2S(0.5) H2Sa(0.5) H2Sb(0.5) C3S(0.5)
 H3Sa(0.5) H3Sb(0.5) C4S(0.5) H4Sa(0.5) H4Sb(0.5) O1S(0.5) O2S(0.25) C8S(0.25)
 H8Sa(0.25) H8Sb(0.25) C7S(0.25) H7Sa(0.25) H7Sb(0.25) C6S(0.25) H6Sa(0.25)
 H6Sb(0.25) C5S(0.25) H5Sa(0.25) H5Sb(0.25)
6.a Ternary CH refined with riding coordinates:
 B1(H1)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3a,H3b), C2(H2a,H2b), C11S(H11b,H11c), C10S(H10b,H10c), C1S(H1Sa,H1Sb),
 C2S(H2Sa,H2Sb), C3S(H3Sa,H3Sb), C4S(H4Sa,H4Sb), C8S(H8Sa,H8Sb), C7S(H7Sa,H7Sb),
  C6S(H6Sa,H6Sb), C5S(H5Sa,H5Sb)
6.c Aromatic/amide H refined with riding coordinates:
 C42A(H42A), C6A(H6A), C18A(H18A), C26A(H26A), C14A(H14A), C36A(H36A),
 C2A(H2Aa), C12A(H12A), C44A(H44A), C45A(H45A), C46A(H46A), C47A(H47A),
 C48A(H48A), C4A(H4A), C32A(H32A), C38A(H38A), C35A(H35A), C17A(H17A),
 C11A(H11A), C34A(H34A), C24A(H24A), C27A(H27A), C40A(H40A), C3A(H3Aa),
 C15A(H15A), C5A(H5A), C33A(H33A), C10A(H10A), C41A(H41A), C39A(H39A), C8A(H8A),
  C20A(H20A), C22A(H22A), C16A(H16A), C9A(H9A), C23A(H23A), C21A(H21A),
 C29A(H29A), C28A(H28A), C30A(H30A)
6.d Fitted hexagon refined as free rotating group:
 C43A(C44A,C45A,C46A,C47A,C48A)
6.e Idealised Me refined as rotating group:
 C9S(H9Sa,H9Sb,H9Sc), C12S(H12b,H12c,H12d)
;
_shelx_res_checksum              87020
_shelx_hkl_checksum              8711
_olex2_submission_special_instructions 'No special instructions were received'