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_4087806
_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 H20 Cl2 F4 N2 Pd2'
_chemical_formula_sum            'C18 H20 Cl2 F4 N2 Pd2'
_chemical_formula_weight         624.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-10-03
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9534(19)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.67526(12)
_cell_length_b                   26.5650(6)
_cell_length_c                   6.85327(14)
_cell_measurement_reflns_used    7391
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.9760
_cell_measurement_theta_min      3.0640
_cell_volume                     1029.36(4)
_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 0.999
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_details
;
  1 omega  -98.00   19.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740  -19.0000 -120.0000 117

  2 omega  -45.00   44.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0740   57.0000   60.0000 89

  3 omega   -4.00   79.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802 -118.0000  155.0000 83

  4 omega  -42.00   48.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802  -57.0000 -180.0000 90

  5 omega  -20.00   68.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802  -99.0000  -30.0000 88

  6 omega   21.00  102.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802 -160.0000    3.0000 81

  7 omega    6.00   95.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802   57.0000 -150.0000 89

  8 omega    6.00   95.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4802   57.0000  120.0000 89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0060296000
_diffrn_orient_matrix_UB_12      -0.0249801000
_diffrn_orient_matrix_UB_13      0.0358406000
_diffrn_orient_matrix_UB_21      -0.0339789000
_diffrn_orient_matrix_UB_22      -0.0086798000
_diffrn_orient_matrix_UB_23      -0.0962087000
_diffrn_orient_matrix_UB_31      0.1205815000
_diffrn_orient_matrix_UB_32      -0.0036991000
_diffrn_orient_matrix_UB_33      -0.0159690000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            18211
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.153
_diffrn_reflns_theta_min         3.067
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.048
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.798
_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    2.013
_exptl_crystal_description
;
;
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.4419
_exptl_crystal_size_mid          0.0621
_exptl_crystal_size_min          0.0294
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.951
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.352
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         3380
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.352
_refine_ls_R_factor_all          0.0428
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0038P)^2^+2.0683P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3149
_reflns_number_total             3380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00608_si_002.cif
_cod_data_source_block           3d_ijsf1452
_cod_database_code               4087806
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C18 H20 Cl2 F4 N2 Pd2'
_chemical_oxdiff_usercomment     'Jessica Milani JM-C-200-1'
_reflns_odcompleteness_completeness 99.86
_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:
 C3(H3), C4(H4)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_olex2_exptl_crystal_mounting_method 'oil on loop'
_olex2_submission_original_sample_id JM-C-200-1
_olex2_submission_special_instructions 'No special instructions were received'