The Role of Fluorine Substituents in the Regioselectivity of Intramolecular C‒H Bond Functionalization of Benzylamines at Palladium(II)
Milani, Jessica; Pridmore, Natalie E.; Whitwood, Adrian C.; Fairlamb, Ian J. S.; Perutz, Robin N.; Organometallics 34 (2015) 4376–; doi:10.1021/acs.organomet.5b00608

data_4087811
_publ_section_title
;
 The Role of Fluorine Substituents in the Regioselectivity of
 Intramolecular C--H Bond Functionalization of Benzylamines at
 Palladium(II)
;
_journal_issue                   17
_journal_name_full               Organometallics
_journal_page_first              4376
_journal_paper_doi               10.1021/acs.organomet.5b00608
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C18 H22 Cl2 F2 N2 Pd2'
_chemical_formula_sum            'C18 H22 Cl2 F2 N2 Pd2'
_chemical_formula_weight         588.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.06 svn.r3119 for OlexSys, GUI svn.r4979)
;
_cell_angle_alpha                70.599(9)
_cell_angle_beta                 72.092(9)
_cell_angle_gamma                80.881(8)
_cell_formula_units_Z            1
_cell_length_a                   7.1636(7)
_cell_length_b                   8.0381(8)
_cell_length_c                   9.4603(9)
_cell_measurement_reflns_used    2736
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.9560
_cell_measurement_theta_min      4.1400
_cell_volume                     487.95(9)
_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  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.888
_diffrn_measurement_details
;
  1 omega  -20.00   57.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -99.0000   60.0000 77

  2 omega   11.00   69.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797 -103.0000  160.0000 58

  3 omega  -34.00   87.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797    0.0000 -150.0000 121

  4 omega  -39.00   39.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       25.4797  -57.0000 -180.0000 78

  5 omega  -69.00   -9.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -26.1047  103.0000  -97.0000 60

  6 omega  -95.00  -58.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -26.1047 -178.0000  -90.0000 37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0218815000
_diffrn_orient_matrix_UB_12      0.0277042000
_diffrn_orient_matrix_UB_13      0.0674459000
_diffrn_orient_matrix_UB_21      -0.0641266000
_diffrn_orient_matrix_UB_22      -0.0695682000
_diffrn_orient_matrix_UB_23      0.0419566000
_diffrn_orient_matrix_UB_31      0.0792436000
_diffrn_orient_matrix_UB_32      -0.0563893000
_diffrn_orient_matrix_UB_33      0.0228208000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.888
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            5092
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.888
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.140
_diffrn_reflns_theta_min         3.273
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.139
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_correction_T_min  0.737
_exptl_absorpt_correction_type   analytical
_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)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.001
_exptl_crystal_description       irregular
_exptl_crystal_F_000             288
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.1067
_exptl_crystal_size_min          0.0992
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     120
_refine_ls_number_reflns         3033
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0296
_refine_ls_R_factor_gt           0.0257
_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^)+(0.0186P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0522
_refine_ls_wR_factor_ref         0.0557
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2791
_reflns_number_total             3033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00608_si_002.cif
_cod_data_source_block           3c6_rnp1501
_cod_database_code               4087811
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C18 H22 Cl2 F2 N2 Pd2'
_chemical_oxdiff_usercomment     'Jess Milani JM-C-254'
_reflns_odcompleteness_completeness 99.10
_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 Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_olex2_date_sample_data_collection 2015-01-09
_olex2_exptl_crystal_mounting_method 'oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'