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_7116784
_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_formula_moiety         'C14 H15 N4 O Pd, 2(F3 P0.5)'
_chemical_formula_sum            'C14 H15 F6 N4 O P Pd'
_chemical_formula_weight         506.67
_chemical_name_systematic        3.PF6
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_symmetry_space_group_name_Hall  '-P 2yb'
_symmetry_space_group_name_H-M   'P 1 21/m 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                 91.882(17)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.097(3)
_cell_length_b                   6.8619(13)
_cell_length_c                   21.461(3)
_cell_measurement_reflns_used    1380
_cell_measurement_temperature    100.2(7)
_cell_measurement_theta_max      71.0660
_cell_measurement_theta_min      3.6460
_cell_volume                     1780.5(6)
_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      100.2(7)
_diffrn_detector_area_resol_mean 5.3095
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
  1 omega  -47.00   32.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000  -60.0000 79

  2 omega  -25.00   29.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000   60.0000 54

  3 omega  -50.00  -13.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -64.0000  -56.4656 37

  4 omega   10.00   66.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       42.2089  -57.0000  -90.0000 56

  5 omega   31.00   68.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       42.2089  -65.0000  129.8815 37

  6 omega   17.00   67.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       42.2089  -57.0000 -180.0000 50

  7 omega   58.00  115.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -65.0000 -150.6782 57

  8 omega   68.00   96.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -64.0000  -66.5924 28

  9 omega   63.00  126.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -65.0000 -114.6840 63

 10 omega   35.00   75.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -30.0000 -180.0000 40

 11 omega   59.00  104.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -65.0000  123.0670 45

 12 omega   30.00  103.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -15.0000 -150.0000 73

 13 omega   85.00  174.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492   45.0000    0.0000 89

 14 omega   68.00   93.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -64.0000  -80.7060 25

 15 omega   37.00  105.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -      104.6492  -65.0000  160.9911 68
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0027004000
_diffrn_orient_matrix_UB_12      -0.0143508000
_diffrn_orient_matrix_UB_13      -0.0717377000
_diffrn_orient_matrix_UB_21      -0.0025304000
_diffrn_orient_matrix_UB_22      0.2234813000
_diffrn_orient_matrix_UB_23      -0.0044898000
_diffrn_orient_matrix_UB_31      0.1274014000
_diffrn_orient_matrix_UB_32      0.0047061000
_diffrn_orient_matrix_UB_33      0.0007894000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0681
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            6445
_diffrn_reflns_theta_full        55.10
_diffrn_reflns_theta_max         55.10
_diffrn_reflns_theta_min         3.66
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.960
_exptl_absorpt_correction_T_max  0.752
_exptl_absorpt_correction_T_min  0.431
_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    1.890
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.594
_refine_diff_density_min         -1.202
_refine_diff_density_rms         0.186
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         2419
_refine_ls_number_restraints     712
_refine_ls_restrained_S_all      0.954
_refine_ls_R_factor_all          0.1697
_refine_ls_R_factor_gt           0.1449
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1333P)^2^+61.8453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3606
_refine_ls_wR_factor_ref         0.3755
_reflns_number_gt                1747
_reflns_number_total             2419
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4cc10163d2.cif
_cod_data_source_block           mrc090b
_cod_original_cell_volume        1780.4(6)
_cod_database_code               7116784
_chemical_oxdiff_formula         'C56 H60 F24 N16 O4 P4 Pd4'
_reflns_odcompleteness_completeness 98.02
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
Uanis(N3) = Uanis(N7)
4. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H12B(0.5) H12C(0.5) H14B(0.5) H14C(0.5) C15(0.5)
 H15(0.5) C16(0.5) H16(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5) H28B(0.5)
 H28C(0.5) F5(0.75) F6(0.75) F7(0.75) F8(0.75) C17(0.5) H17A(0.5) H17B(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C17(H17A,H17B)
5.b Me refined with riding coordinates:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C26(H26A,H26B,H26C), C28(H28A,H28B,
 H28C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C8(H8), C10(H10), C11(H11), C15(H15),
 C16(H16), C19(H19), C20(H20), C22(H22), C24(H24), C25(H25)
;
_olex2_submission_special_instructions 'No special instructions were received'