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_4087804
_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_absolute_configuration ad
_chemical_formula_moiety         'C22 H28 F2 N2 O4 Pd2'
_chemical_formula_sum            'C22 H28 F2 N2 O4 Pd2'
_chemical_formula_weight         635.26
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-16
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 106.0050(17)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   8.34276(13)
_cell_length_b                   14.9448(2)
_cell_length_c                   9.77429(16)
_cell_measurement_reflns_used    9870
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      32.0923
_cell_measurement_theta_min      2.8430
_cell_volume                     1171.43(3)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9986
_diffrn_measured_fraction_theta_max 0.9860
_diffrn_measurement_details
;
  1 omega  -89.00  -63.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -25.0110 -178.0000  120.0000 26

  2 omega   44.00   82.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172 -178.0000   90.0000 38

  3 omega  -18.00   98.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   19.0000  -90.0000 116

  4 omega  -47.00    9.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -19.0000  -90.0000 56

  5 omega   34.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172 -178.0000 -150.0000 69

  6 omega  -42.00   47.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172  -57.0000 -120.0000 89

  7 omega    5.00   30.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   57.0000  -60.0000 25

  8 omega   -4.00   97.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       26.4172   77.0000    0.0000 101
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0152108000
_diffrn_orient_matrix_UB_12      0.0322419000
_diffrn_orient_matrix_UB_13      -0.0481947000
_diffrn_orient_matrix_UB_21      -0.0806322000
_diffrn_orient_matrix_UB_22      0.0182364000
_diffrn_orient_matrix_UB_23      -0.0083317000
_diffrn_orient_matrix_UB_31      0.0330122000
_diffrn_orient_matrix_UB_32      0.0296638000
_diffrn_orient_matrix_UB_33      0.0575063000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14799
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         32.16
_diffrn_reflns_theta_min         2.85
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.581
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.876
_exptl_absorpt_correction_type   analytical
_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)
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)
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.801
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_recrystallization_method chloroform/hexane
_exptl_crystal_size_max          0.2526
_exptl_crystal_size_mid          0.1866
_exptl_crystal_size_min          0.1103
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.031(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         7245
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0151P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0501
_refine_ls_wR_factor_ref         0.0520
_reflns_number_gt                6922
_reflns_number_total             7245
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            om5b00608_si_002.cif
_cod_data_source_block           2b_ijsf1301
_cod_database_code               4087804
_chemical_oxdiff_formula         'C22 H28 F2 N2 O4 Pd2'
_chemical_oxdiff_usercomment     'Jessica's JM-A-2S'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H16A,H16B} of C16, H4 of C4, H3 of C3, H11 of C11, {H7A,H7B} of C7, H12 of
  C12, H2 of C2, H13 of C13
 At 1.5 times of:
  {H9A,H9B,H9C} of C9, {H8A,H8B,H8C} of C8, {H20A,H20B,H20C} of C20, {H17A,
  H17B,H17C} of C17, {H18A,H18B,H18C} of C18, {H22A,H22B,H22C} of C22
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C2(H2), C12(H12), C11(H11), C3(H3), C4(H4)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C18(H18A,H18B,H18C), C8(H8A,H8B,H8C), C20(H20A,H20B,
 H20C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C)
;