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_4087802
_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         'C22 H30 N2 O4 Pd2'
_chemical_formula_sum            'C22 H30 N2 O4 Pd2'
_chemical_formula_weight         599.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.06 svn.r3119 for OlexSys, GUI svn.r4979)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.8594(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.31342(13)
_cell_length_b                   20.6214(2)
_cell_length_c                   13.02840(18)
_cell_measurement_reflns_used    12827
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      32.1984
_cell_measurement_theta_min      2.9575
_cell_volume                     2338.18(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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_temperature      109.95(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.919
_diffrn_measurement_details
;
  1 omega  -80.00  -38.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.1672  121.0000  -64.0000 42

  2 omega  -35.00   -9.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.1672  121.0000  -64.0000 26

  3 omega  -49.00  -23.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.1672  121.0000  -33.0000 26

  4 omega    3.00   81.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172 -121.0000 -146.0000 78

  5 omega    7.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   57.0000  120.0000 82

  6 omega  -41.00   38.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -57.0000 -120.0000 79

  7 omega  -18.00   96.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   19.0000   60.0000 114
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0290447000
_diffrn_orient_matrix_UB_12      -0.0287316000
_diffrn_orient_matrix_UB_13      -0.0155147000
_diffrn_orient_matrix_UB_21      0.0450554000
_diffrn_orient_matrix_UB_22      -0.0060047000
_diffrn_orient_matrix_UB_23      0.0558495000
_diffrn_orient_matrix_UB_31      -0.0613246000
_diffrn_orient_matrix_UB_32      -0.0179398000
_diffrn_orient_matrix_UB_33      0.0061262000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.919
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            26130
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         32.271
_diffrn_reflns_theta_min         3.063
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.567
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92628
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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    1.702
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.2346
_exptl_crystal_size_mid          0.1923
_exptl_crystal_size_min          0.1448
_refine_diff_density_max         1.681
_refine_diff_density_min         -1.583
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Flack x determined using 5342 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.005(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.228
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     553
_refine_ls_number_reflns         14096
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.228
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0442
_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^)+6.8425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0868
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.777
_reflns_number_gt                12899
_reflns_number_total             14096
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00608_si_002.cif
_cod_data_source_block           2a_ijsf1206c
_cod_database_code               4087802
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C22 H30 N2 O4 Pd2'
_chemical_oxdiff_usercomment     'Jessica JM A 16 '
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_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), C16(H16A,H16B), C29(H29A,H29B), C38(H38A,H38B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14),
 C24(H24), C25(H25), C26(H26), C27(H27), C33(H33), C34(H34), C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C44(H44A,
 H44B,H44C)
;
_olex2_date_sample_data_collection 2012-06-15
_olex2_submission_special_instructions 'No special instructions were received'