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_4087807
_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         '2(C9 H12 F2 N), Cl4 Pd'
_chemical_formula_sum            'C18 H24 Cl4 F4 N2 Pd'
_chemical_formula_weight         592.59
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-09-19
_audit_creation_method
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Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                88.359(7)
_cell_angle_beta                 83.544(9)
_cell_angle_gamma                62.039(10)
_cell_formula_units_Z            1
_cell_length_a                   7.6283(8)
_cell_length_b                   8.0141(6)
_cell_length_c                   10.8354(10)
_cell_measurement_reflns_used    2093
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      31.4600
_cell_measurement_theta_min      3.3600
_cell_volume                     581.16(11)
_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
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
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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 0.890
_diffrn_measurement_details
;
  1 omega  -37.00   39.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802  -57.0000    0.0000 76

  2 omega   49.00   76.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802 -114.0000   75.0000 27

  3 omega   22.00   66.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802  -99.0000  120.0000 44

  4 omega   -9.00   68.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802  -99.0000  -60.0000 77

  5 omega  -18.00   99.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802   19.0000 -180.0000 117

  6 omega    7.00   90.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       26.4802   57.0000 -120.0000 83
;
_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      0.0154072000
_diffrn_orient_matrix_UB_12      -0.0818544000
_diffrn_orient_matrix_UB_13      -0.0329273000
_diffrn_orient_matrix_UB_21      -0.0253561000
_diffrn_orient_matrix_UB_22      -0.0357813000
_diffrn_orient_matrix_UB_23      0.0559705000
_diffrn_orient_matrix_UB_31      -0.1016989000
_diffrn_orient_matrix_UB_32      0.0454732000
_diffrn_orient_matrix_UB_33      -0.0112442000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.890
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5930
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         32.119
_diffrn_reflns_theta_min         2.876
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.297
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.841
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.693
_exptl_crystal_description       plate
_exptl_crystal_F_000             296
_exptl_crystal_size_max          0.2161
_exptl_crystal_size_mid          0.1457
_exptl_crystal_size_min          0.0405
_refine_diff_density_max         1.653
_refine_diff_density_min         -1.231
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         3635
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0461
_refine_ls_R_factor_gt           0.0386
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0368P)^2^+0.0631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0884
_refine_ls_wR_factor_ref         0.0951
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3217
_reflns_number_total             3635
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00608_si_002.cif
_cod_data_source_block           1dH+_ijsf1452a
_cod_database_code               4087807
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C18 H24 Cl4 F4 N2 Pd'
_reflns_odcompleteness_completeness 99.92
_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:
 C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C)
;
_shelx_res_checksum              28142
_shelx_hkl_checksum              5936
_olex2_exptl_crystal_mounting_method 'Oil on loop'
_olex2_submission_special_instructions 'No special instructions were received'