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_7117135
_publ_section_title
;
 Intramolecular transcyclometallation: the exchange of an aryl-Pt bond for
 an alkyl-Pt bond via an agostic intermediate
;
_journal_coden_Cambridge         182
_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
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-01-26
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2853 for OlexSys, GUI svn.r4736)
;
_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            8
_cell_length_a                   14.9738(3)
_cell_length_b                   15.8809(4)
_cell_length_c                   24.6498(8)
_cell_measurement_reflns_used    12617
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.9770
_cell_measurement_theta_min      3.3080
_cell_volume                     5861.7(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS-2013 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.936
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0028563000
_diffrn_orient_matrix_UB_12      0.0445516000
_diffrn_orient_matrix_UB_13      0.0009366000
_diffrn_orient_matrix_UB_21      0.0195267000
_diffrn_orient_matrix_UB_22      0.0001407000
_diffrn_orient_matrix_UB_23      -0.0262412000
_diffrn_orient_matrix_UB_31      -0.0430238000
_diffrn_orient_matrix_UB_32      0.0030406000
_diffrn_orient_matrix_UB_33      -0.0118353000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            45707
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.168
_diffrn_reflns_theta_min         3.008
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.056
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35142
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.662
_exptl_crystal_description       block
_exptl_crystal_F_000             2896
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.003
_refine_diff_density_max         1.166
_refine_diff_density_min         -1.423
_refine_diff_density_rms         0.120
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         8857
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0467
_refine_ls_R_factor_gt           0.0309
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0185P)^2^+8.0820P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0562
_refine_ls_wR_factor_ref         0.0611
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                6926
_reflns_number_total             8857
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc02355f2.cif
_cod_data_source_block           ps2
_cod_database_code               7117135
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C20 H20 N2 O2 F P Pt'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.64
_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. Rigid bond restraints
 C27, C28A, C29A
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 1.7
 C23, C24, C25, C25A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 1.7
3. Uiso/Uaniso restraints and constraints
C27 \\sim C28A \\sim C29A: within 1.7A with sigma of 0.002 and sigma for
terminal atoms of 0.008
C23 \\sim C24 \\sim C25 \\sim C25A: within 1.7A with sigma of 0.002 and sigma
for terminal atoms of 0.008
Uanis(C29) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.016
4. Others
 Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(H27C)=
 Sof(H27D)=1-FVAR(1)
 Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(H27A)=
 Sof(H27B)=Sof(C28)=FVAR(1)
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(2)
 Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B), C24(H24C,H24D), C26(H26A,H26B), C27(H27A,H27B),
 C27(H27C,H27D), C28(H28A,H28B), C28A(H28C,H28D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C14(H14), C16(H16), C17(H17)
5.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C), C25A(H25D,H25E,H25F), C29(H29A,H29B,
 H29C), C29A(H29D,H29E,H29F)
;