How Does Palladium Coordination Affect the Electrophilicities of Allyl Cations? Development of a Robust Kinetic Method for Following Reactions of [(η3-Diarylallyl)Pd(PPh3)2]+with Nucleophiles
Troshin, Konstantin; Mayer, Peter; Mayr, Herbert; Organometallics 31 (2012) 2416–; doi:10.1021/om3000357

data_4076566
_publ_section_title
;
 How Does Palladium Coordination Affect the Electrophilicities of Allyl
 Cations? Development of a Robust Kinetic Method for Following Reactions
 of [(\h3-Diarylallyl)Pd(PPh3)2]+with Nucleophiles
;
_journal_issue                   6
_journal_name_full               Organometallics
_journal_page_first              2416
_journal_paper_doi               10.1021/om3000357
_journal_volume                  31
_journal_year                    2012
_chemical_formula_moiety         'C51 H39 F4 P2 Pd, 2(C3 H6 O), C F3 O3 S'
_chemical_formula_sum            'C58 H51 F7 O5 P2 Pd S'
_chemical_formula_weight         1161.44
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_block_code
Pd_PPh3_C3H3C6H3F2C6H3F2_CF3SO3_acetone_po010_mayr
_audit_creation_date
;
'Tue Jan 18 12:41:53 2011'
;
_audit_creation_method           'form98_non/compatible with shelxl97-2'
_audit_update_record             18-Jan-11
_cell_angle_alpha                76.998(3)
_cell_angle_beta                 76.763(3)
_cell_angle_gamma                81.982(3)
_cell_formula_units_Z            2
_cell_length_a                   10.9466(4)
_cell_length_b                   12.2758(4)
_cell_length_c                   21.0419(8)
_cell_measurement_reflns_used    8351
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      26.2497
_cell_measurement_theta_min      4.1626
_cell_volume                     2670.32(17)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET)
(compiled May  6 2009,17:20:42)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET)
(compiled May  6 2009,17:20:42)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET)
(compiled May  6 2009,17:20:42)
;
_computing_structure_refinement
;
Sheldrick, G. M. (2008).
<i>Acta Cryst.</i> A<b>64</b>, 112--122.
;
_computing_structure_solution
;
A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A.
Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna: SIR97: a new tool for
crystal structure determination and refinement; J. Appl. Crystallogr. 1999,
32, 115-119.
;
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 15.9809
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega  -24.00    8.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.4940  -38.0000  -30.0000 32

  2 omega   -4.00   85.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5878   77.0000  -90.0000 89

  3 omega  -52.00   47.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5878  -77.0000    0.0000 99

  4 omega   36.00   65.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5878  179.0000 -180.0000 29

  5 omega  -31.00   45.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5878  -77.0000 -150.0000 76

  6 omega   -9.00   81.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       18.5878   77.0000  120.0000 90

;
_diffrn_measurement_device       'CCD camera on \k-goniostat'
_diffrn_measurement_device_type  'Oxford XCalibur'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0552073382
_diffrn_orient_matrix_UB_12      -0.0221151308
_diffrn_orient_matrix_UB_13      -0.0198611313
_diffrn_orient_matrix_UB_21      0.0133306459
_diffrn_orient_matrix_UB_22      0.0551788948
_diffrn_orient_matrix_UB_23      -0.0169731744
_diffrn_orient_matrix_UB_31      0.0352111311
_diffrn_orient_matrix_UB_32      0.0032383298
_diffrn_orient_matrix_UB_33      0.0238173967
_diffrn_radiation_collimation    '0.5 mm collimator'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_sigmaI/netI    0.0805
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            21987
_diffrn_reflns_theta_full        26.33
_diffrn_reflns_theta_max         26.33
_diffrn_reflns_theta_min         4.17
_diffrn_source_current           40_mA
_diffrn_source_power             2.00_kW
_diffrn_source_type              'Spellman generator'
_diffrn_source_voltage           50_kV
_exptl_absorpt_coefficient_mu    0.519
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET)
(compiled May  6 2009,17:20:42)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.44451(9)
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.891
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     671
_refine_ls_number_reflns         10816
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.891
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0268P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0673
_refine_ls_wR_factor_ref         0.0709
_reflns_number_gt                7710
_reflns_number_total             10816
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om3000357_si_002.cif
_cod_data_source_block           po010
_cod_database_code               4076566