Heterolytic carbon–iodine bond cleavage by a palladium(i) metalloradical
Sinclair, Matthew J. G.; Chaplin, Adrian B.; Dalton Transactions  (2022) –; doi:10.1039/D2DT02152H

data_7710762
_publ_section_title
;
 Heterolytic carbon--iodine bond cleavage by a palladium(i) metalloradical
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02152H
_journal_year                    2022
_chemical_formula_moiety         'C31 H61 O P2 Pd, F6 P'
_chemical_formula_sum            'C31 H61 F6 O P3 Pd'
_chemical_formula_weight         763.10
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-01-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-16 deposited with the CCDC.	2022-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.7944(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.1657(4)
_cell_length_b                   15.01941(18)
_cell_length_c                   17.2918(2)
_cell_measurement_reflns_used    43012
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.2360
_cell_measurement_theta_min      3.9280
_cell_volume                     7251.62(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -115.00 -20.00   1.00    2.50    --  -42.36 -37.00 120.00   95
  2  \w    -96.00  -2.00   1.00    2.50    --  -42.36 125.00 -90.00   94
  3  \w   -115.00 -20.00   1.00    2.50    --  -42.36 -37.00-180.00   95
  4  \w     23.00  97.00   1.00    2.50    --   42.36-125.00 -90.00   74
  5  \w     94.00 178.00   1.00   10.00    --  106.00 125.00 -60.00   84
  6  \w     32.00 137.00   1.00   10.00    --  106.00 -77.00 120.00  105
  7  \w     78.00 176.00   1.00   10.00    --  106.00  61.00  30.00   98
  8  \w     78.00 176.00   1.00   10.00    --  106.00  61.00 -30.00   98
  9  \w     78.00 176.00   1.00   10.00    --  106.00  61.00 -90.00   98
 10  \w     25.00 109.00   1.00   10.00    --  106.00 -94.00-180.00   84
 11  \w     75.00 178.00   1.00   10.00    --  106.00  77.00 -90.00  103
 12  \w     32.00 137.00   1.00   10.00    --  106.00 -77.00-120.00  105
 13  \w     61.00 178.00   1.00   10.00    --  106.00  15.00   0.00  117
 14  \w     25.00 109.00   1.00   10.00    --  106.00 -94.00-150.00   84
 15  \w     94.00 178.00   1.00   10.00    --  106.00 125.00-120.00   84
 16  \w     94.00 178.00   1.00   10.00    --  106.00 125.00 -30.00   84
 17  \w     94.00 178.00   1.00   10.00    --  106.00 125.00-150.00   84
 18  \w   -116.00 -11.00   1.00    2.50    --  -42.36 -77.00 120.00  105
 19  \w   -116.00 -11.00   1.00    2.50    --  -42.36 -77.00 -60.00  105
 20  \w   -116.00 -11.00   1.00    2.50    --  -42.36 -77.00  30.00  105
 21  \w     78.00 176.00   1.00   10.00    --  106.00  61.00-150.00   98
 22  \w     78.00 176.00   1.00   10.00    --  106.00  61.00  90.00   98
 23  \w     25.00 109.00   1.00   10.00    --  106.00 -94.00  30.00   84
 24  \w     78.00 176.00   1.00   10.00    --  106.00  61.00  60.00   98
 25  \w     78.00 176.00   1.00   10.00    --  106.00  61.00 120.00   98
 26  \w     78.00 164.00   1.00   10.00    --  106.00  61.00-180.00   86
 27  \w     82.00 178.00   1.00   10.00    --  106.00  30.00-180.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku Oxford Diffraction: SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0222804000
_diffrn_orient_matrix_UB_12      0.0927108000
_diffrn_orient_matrix_UB_13      -0.0231856000
_diffrn_orient_matrix_UB_21      0.0158689000
_diffrn_orient_matrix_UB_22      0.0276049000
_diffrn_orient_matrix_UB_23      0.0895516000
_diffrn_orient_matrix_UB_31      0.0478847000
_diffrn_orient_matrix_UB_32      0.0339638000
_diffrn_orient_matrix_UB_33      -0.0095236000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            63692
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        70.076
_diffrn_reflns_theta_max         70.076
_diffrn_reflns_theta_min         6.341
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.842
_exptl_absorpt_correction_T_max  0.853
_exptl_absorpt_correction_T_min  0.596
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             3200
_exptl_crystal_recrystallization_method
'Crystals grown from 1,2-F2C6H4/hexane at 293 K'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.048
_refine_diff_density_max         1.294
_refine_diff_density_min         -0.907
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1020
_refine_ls_number_reflns         13733
_refine_ls_number_restraints     1649
_refine_ls_restrained_S_all      1.192
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0381P)^2^+38.5951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1400
_refine_ls_wR_factor_ref         0.1433
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12310
_reflns_number_total             13733
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02152h2.cif
_cod_data_source_block           0364abc18s
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        7251.64(16)
_cod_database_code               7710762
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P5-F7 \\sim P5-F8 \\sim P5-F9 \\sim P5-F10 \\sim P5-F11 \\sim P5-F12 \\sim
P5-F7A \\sim P5-F8A \\sim P5-F9A ~
 P5-F10A \\sim P5-F11A \\sim P5-F12A
 with sigma of 0.01
 F7-F9 \\sim F7-F10 \\sim F7-F11 \\sim F7-F12 \\sim F8-F9 \\sim F8-F10 \\sim
F8-F11 \\sim F8-F12 \\sim F9-F11
 \\sim F9-F12 \\sim F10-F11 \\sim F10-F12 \\sim F7A-F9A \\sim F7A-F10A \\sim
F7A-F11A \\sim F7A-F12A \\sim F8A-
 F9A \\sim F8A-F10A \\sim F8A-F11A \\sim F8A-F12A \\sim F9A-F11A \\sim F9A-F12A
\\sim F10A-F11A \\sim F10A-
 F12A
 with sigma of 0.01
 C13-O18 \\sim C13A-O18A
 with sigma of 0.01
 O18-C19 \\sim O18A-C19A
 with sigma of 0.01
 P2-C20 \\sim P2-C20A \\sim P2-C28 \\sim P2-C28A \\sim P2-C24 \\sim P2-C24A
 with sigma of 0.01
 C22A-C20A \\sim C23A-C20A \\sim C21A-C20A \\sim C23-C20 \\sim C21-C20 \\sim
C22-C20 \\sim C29-C28 ~
 C30-C28 \\sim C31-C28 \\sim C31A-C28A \\sim C29A-C28A \\sim C30A-C28A \\sim
C25-C24 \\sim C26-C24 ~
 C27-C24 \\sim C25A-C24A \\sim C27A-C24A \\sim C26A-C24A
 with sigma of 0.01
 C21-C22 \\sim C22-C23 \\sim C23-C21 \\sim C25-C26 \\sim C26-C27 \\sim C27-C25
\\sim C29-C30 \\sim C30-C31
 \\sim C31-C29 \\sim C21A-C22A \\sim C22A-C23A \\sim C23A-C21A \\sim C25A-C26A
\\sim C26A-C27A \\sim C27A-
 C25A \\sim C29A-C30A \\sim C30A-C31A \\sim C31A-C29A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C17A \\sim C12A \\sim C12 \\sim C17 \\sim O18A \\sim C19A \\sim C16 \\sim C15
\\sim C13 \\sim C13A \\sim C14A \\sim C14 \\sim C15A \\sim C16A \\sim C19 \\sim
O18 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim
C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C20A \\sim C21A \\sim C22A
\\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A
\\sim C30A \\sim C31A \\sim P5 \\sim F7A \\sim F8A \\sim F9A \\sim F10A \\sim
F11A \\sim F12A \\sim F7 \\sim F8 \\sim F9 \\sim F10 \\sim F11 \\sim F12:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C17A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(O18A) \\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C16) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C16A) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(O18) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C28A) \\sim Ueq,
Uanis(C29A) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(P5)
\\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9A) \\sim Ueq,
Uanis(F10A) \\sim Ueq, Uanis(F11A) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F7)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq,
Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq: with sigma of 0.006 and sigma for
terminal atoms of 0.012
4. Others
 Sof(O18A)=Sof(C13A)=Sof(C14A)=Sof(H14J)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C12A)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=1-FVAR(1)
 Sof(O18)=Sof(C12)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=Sof(C15)=Sof(H15)=
 Sof(C14)=Sof(H14)=Sof(C13)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(1)
 Sof(C28A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(2)
 Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(2)
 Sof(C24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(3)
 Sof(C24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(3)
 Sof(C20A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22A)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(4)
 Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(5)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(5)
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C17(H17), C16(H16), C15(H15), C14(H14),
 C14A(H14J), C15A(H15A), C16A(H16A), C17A(H17A)
5.b Fitted hexagon refined as free rotating group:
 C12(C17,C16,C15,C14,C13), C13A(C14A,C15A,C16A,C17A,C12A)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C21A(H21D,H21E,H21F), C22A(H22D,H22E,H22F), C23A(H23D,H23E,H23F),
 C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F), C29A(H29D,
 H29E,H29F), C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F), C121(H12A,H12B,H12C),
 C122(H12D,H12E,H12F), C123(H12G,H12H,H12I), C125(H12J,H12K,H12L), C126(H12M,
 H12N,H12O), C127(H12P,H12Q,H12R), C129(H12S,H12T,H12U), C130(H13A,H13B,H13C),
 C131(H13D,H13E,H13F), C133(H13G,H13H,H13I), C134(H13J,H13K,H13L), C135(H13M,
 H13N,H13O), C137(H13P,H13Q,H13R), C138(H13S,H13T,H13U), C139(H13V,H13W,H13X),
 C141(H14A,H14B,H14C), C142(H14D,H14E,H14F), C143(H14G,H14H,H14I), C19(H19A,
 H19B,H19C), C19A(H19D,H19E,H19F)
;
_shelx_res_checksum              15191
_shelx_hkl_checksum              91027
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 6.716
_oxdiff_exptl_absorpt_empirical_full_min 0.556