sigma-Alkenyl endo-palladacycle formation via regiospecific functionalisation of an unreactive NHC-tethered C(sp2)-H bond
Michael R. Chapman; Christopher M. Pask; Alireza Ariafard; Charlotte E. Willans; Chem.Commun. 51 (2015) 5513–; doi:10.1039/C4cc10163D

data_7116785
_publ_section_title
;
 sigma-Alkenyl endo-palladacycle formation via regiospecific
 functionalisation of an unreactive NHC-tethered C(sp2)-H bond
;
_journal_name_full               Chem.Commun.
_journal_page_first              5513
_journal_paper_doi               10.1039/C4cc10163D
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C14 H15 N4 O Pd, F6 Sb'
_chemical_formula_sum            'C14 H15 F6 N4 O Pd Sb'
_chemical_formula_weight         597.45
_chemical_name_systematic        3.SbF6
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2014-10-30 deposited with the CCDC.
2015-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.568(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   13.0668(11)
_cell_length_b                   6.8152(4)
_cell_length_c                   21.0073(18)
_cell_measurement_reflns_used    4250
_cell_measurement_temperature    119.99(18)
_cell_measurement_theta_max      26.7420
_cell_measurement_theta_min      3.1320
_cell_volume                     1870.7(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28e (release 10-06-2013 CrysAlis171 .NET)
(compiled Jun 10 2013,11:58:50)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28e (release 10-06-2013 CrysAlis171 .NET)
(compiled Jun 10 2013,11:58:50)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28e (release 10-06-2013 CrysAlis171 .NET)
(compiled Jun 10 2013,11:58:50)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      119.99(18)
_diffrn_detector_area_resol_mean 5.3095
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -7.00   80.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       13.1072   37.0000  120.0000 87

  2 omega    3.00   79.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       13.1072   57.0000 -150.0000 76

  3 omega  -50.00  -23.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       13.1072  -57.0000  -60.0000 27

  4 omega    7.00   38.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       13.1072  -57.0000  -60.0000 31

  5 omega   -7.00   22.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       13.1072   37.0000   30.0000 29

  6 omega  -19.00    6.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -13.8884  -57.0000 -180.0000 25

  7 omega  -39.00   -2.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -13.8884  -37.0000 -150.0000 37
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0457462000
_diffrn_orient_matrix_UB_12      0.0290639000
_diffrn_orient_matrix_UB_13      0.0157805000
_diffrn_orient_matrix_UB_21      0.0288484000
_diffrn_orient_matrix_UB_22      -0.0315313000
_diffrn_orient_matrix_UB_23      -0.0265710000
_diffrn_orient_matrix_UB_31      -0.0044410000
_diffrn_orient_matrix_UB_32      0.0948446000
_diffrn_orient_matrix_UB_33      -0.0136267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_av_unetI/netI     0.0728
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12591
_diffrn_reflns_theta_full        25.02
_diffrn_reflns_theta_max         25.02
_diffrn_reflns_theta_min         3.14
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.474
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_correction_T_min  0.860
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28e (release 10-06-2013 CrysAlis171 .NET)
(compiled Jun 10 2013,11:58:50)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.121
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.788
_refine_diff_density_min         -2.171
_refine_diff_density_rms         0.289
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         6225
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1393
_refine_ls_R_factor_gt           0.1189
_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^)+(0.1480P)^2^+67.8856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3056
_refine_ls_wR_factor_ref         0.3264
_reflns_number_gt                5147
_reflns_number_total             6225
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4cc10163d2.cif
_cod_data_source_block           mrc139_mo_b2
_cod_database_code               7116785
_chemical_oxdiff_formula         'C14 H15 N4 O1 Pd1 Sb1 F6'
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_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. Restrained distances
 O1-C9
 1.34 with sigma of 0.02
 O1-C12
 1.41 with sigma of 0.01
 C28-C27 = C14-C13
 1.5 with sigma of 0.02
 N8-C27 = N4-C13
 1.1 with sigma of 0.02
 N6-C18 = N5-C18 = N2-C4 = N1-C4
 1.34 with sigma of 0.02
 N1-C5 = N2-C6 = N6-C20 = N5-C19
 1.37 with sigma of 0.02
 C20-C19 = C6-C5
 1.35 with sigma of 0.02
 N3-C7 = N3-C11 = N7-C21 = N7-C25
 1.34 with sigma of 0.02
 Sb2-F11 \\sim Sb2-F7 \\sim Sb2-F8 \\sim Sb2-F9 \\sim Sb2-F10 \\sim Sb2-F12
\\sim Sb1-F3 \\sim Sb1-F4 ~
 Sb1-F6 \\sim Sb1-F5 \\sim Sb1-F2 \\sim Sb1-F1
 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C3(H3A,H3B)
3.b Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C14(H14A,H14B,H14C)
3.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C19(H19), C20(H20), C22(H22), C24(H24), C25(H25), C1(H1),
 C2(H2), C5(H5), C6(H6), C8(H8), C11(H11), C10(H10)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'