Intramolecular transcyclometallation: the exchange of an aryl-Pt bond for an alkyl-Pt bond via an agostic intermediate
Paul A. Shaw; Jessica M. Phillips; Christopher P. Newman; Guy J. Clarkson; Jonathan P. Rourke; Chem.Commun. 51 (2015) 8365–; doi:10.1039/C5cc02355F

data_7117137
_publ_section_title
;
 Intramolecular transcyclometallation: the exchange of an aryl-Pt bond for
 an alkyl-Pt bond via an agostic intermediate
;
_journal_name_full               Chem.Commun.
_journal_page_first              8365
_journal_paper_doi               10.1039/C5cc02355F
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C29 H36 Cl2 F2 N P Pt'
_chemical_formula_sum            'C29 H36 Cl2 F2 N P Pt'
_chemical_formula_weight         733.55
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.21 svn.r3092 for OlexSys, GUI svn.r4949)
;
_audit_update_record
;
2015-03-20 deposited with the CCDC.
2015-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9634(6)
_cell_length_b                   13.9987(4)
_cell_length_c                   11.0698(4)
_cell_measurement_reflns_used    6204
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.0270
_cell_measurement_theta_min      2.9100
_cell_volume                     2783.66(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.904
_diffrn_measurement_details
;
  1 omega  -60.00   36.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141  -38.0000   60.0000 96

  2 omega   -3.00   83.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141   57.0000 -150.0000 86

  3 omega   72.00   98.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141  178.0000   30.0000 26

  4 omega  -14.00   26.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       13.4141   57.0000    0.0000 40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0112153000
_diffrn_orient_matrix_UB_12      0.0420567000
_diffrn_orient_matrix_UB_13      -0.0307734000
_diffrn_orient_matrix_UB_21      0.0374889000
_diffrn_orient_matrix_UB_22      -0.0087281000
_diffrn_orient_matrix_UB_23      0.0168398000
_diffrn_orient_matrix_UB_31      0.0053408000
_diffrn_orient_matrix_UB_32      -0.0268542000
_diffrn_orient_matrix_UB_33      -0.0536236000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0719
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.904
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19220
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.751
_diffrn_reflns_theta_min         2.694
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.323
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.750
_exptl_crystal_description       plate
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.237
_refine_diff_density_min         -0.772
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Flack x determined using 2035 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack   0.016(6)        (Shelxl 2013)
Hooft y parameter 0.005(6)  (Olex2)

;
_refine_ls_abs_structure_Flack   0.016(6)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         7402
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0406
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0248P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0681
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.798
_reflns_number_gt                5493
_reflns_number_total             7402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc02355f2.cif
_cod_data_source_block           ps8n
_cod_database_code               7117137
_chemical_oxdiff_formula         'C20 H20 N2 O2 F2 P Cl2 Pt'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,
 H24B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14),
 C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C), C29(H29A,H29B,H29C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'