Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure.
Becica, Joseph; Gaube, Gregory; Sabbers, William A.; Leitch, David C.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 16067–16071; doi:10.1039/d0dt01119c

data_7704089
_publ_section_title
;
 Oxidative addition of activated aryl-carboxylates to Pd(0): divergent
 reactivity dependant on temperature and structure.
;
_journal_issue                   45
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16067
_journal_page_last               16071
_journal_paper_doi               10.1039/d0dt01119c
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C47 H73.98 O4 P2 Pd, C7 H8'
_chemical_formula_sum            'C54 H81.98 O4 P2 Pd'
_chemical_formula_weight         963.51
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-03-11 deposited with the CCDC.	2020-04-15 downloaded from the CCDC.
;
_cell_angle_alpha                67.8780(10)
_cell_angle_beta                 74.0210(10)
_cell_angle_gamma                86.400(2)
_cell_formula_units_Z            2
_cell_length_a                   13.5548(9)
_cell_length_b                   13.7277(10)
_cell_length_c                   14.8809(10)
_cell_measurement_reflns_used    9792
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.945
_cell_measurement_theta_min      2.188
_cell_volume                     2463.4(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      99.95
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            52734
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.964
_diffrn_reflns_theta_min         1.535
_exptl_absorpt_coefficient_mu    0.486
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6953
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0426 before and 0.0358 after correction. The Ratio of minimum to maximum transmission is 0.9325. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       plate
_exptl_crystal_F_000             1028
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.628
_refine_diff_density_min         -0.850
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     623
_refine_ls_number_reflns         11753
_refine_ls_number_restraints     276
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0428P)^2^+3.0638P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0865
_refine_ls_wR_factor_ref         0.0912
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10331
_reflns_number_total             11753
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01119c2.cif
_cod_data_source_block           solve_a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7704088--7704089.cif.'
_cod_database_code               7704089
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.868
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C53-C54 = C53A-C54A
 0.01 with sigma of 1.5
 C54-C53 = C53A-C54A
 0.02 with sigma of 2.5
 C48-C53 = C49A-C53A
 0.02 with sigma of 2.5
3. Rigid bond restraints
 C54, C53, C48, C49, C50, C51, C52, C54A, C53A, C48A, C49A, C50A, C51A, C52A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C25A, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C25A \\sim C25: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C54 \\sim C53 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C54A
\\sim C53A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25A) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
5. Others
 Sof(H24C)=Sof(H24D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=FVAR(1)
 Sof(H27C)=Sof(H27D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=1-FVAR(2)
 Sof(H27A)=Sof(H27B)=Sof(C26)=Sof(H26A)=Sof(H26B)=FVAR(2)
 Sof(C25A)=Sof(H25C)=Sof(H25D)=1-FVAR(3)
 Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(3)
 Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C53A)=Sof(C52A)=Sof(H52A)=
 Sof(C51A)=Sof(H51A)=Sof(C50A)=Sof(H50A)=Sof(C49A)=Sof(H49A)=Sof(C48A)=
 Sof(H48A)=1-FVAR(4)
 Sof(C53)=Sof(C52)=Sof(H52)=Sof(C51)=Sof(H51)=Sof(C50)=Sof(H50)=Sof(C49)=
 Sof(H49)=Sof(C48)=Sof(H48)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C34(H34), C10(H10), C16(H16), C40(H40), C28(H28), C22(H22)
6.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C36(H36A,H36B), C35(H35A,H35B), C11(H11A,H11B), C19(H19A,
 H19B), C18(H18A,H18B), C17(H17A,H17B), C41(H41A,H41B), C12(H12A,H12B),
 C39(H39A,H39B), C38(H38A,H38B), C33(H33A,H33B), C29(H29A,H29B), C42(H42A,H42B),
  C21(H21A,H21B), C43(H43A,H43B), C30(H30A,H30B), C45(H45A,H45B), C37(H37A,
 H37B), C27(H27A,H27B), C27(H27C,H27D), C13(H13A,H13B), C15(H15A,H15B),
 C31(H31A,H31B), C44(H44A,H44B), C32(H32A,H32B), C14(H14A,H14B), C26(H26A,H26B),
  C24(H24A,H24B), C24(H24C,H24D), C25(H25A,H25B), C23(H23A,H23B), C23A(H23C,
 H23D), C26A(H26C,H26D), C25A(H25C,H25D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C9(H9), C8(H8), C52(H52), C51(H51), C50(H50),
 C49(H49), C48(H48), C52A(H52A), C51A(H51A), C50A(H50A), C49A(H49A), C48A(H48A)
6.d Fitted hexagon refined as free rotating group:
 C53(C52,C51,C50,C49,C48), C53A(C52A,C51A,C50A,C49A,C48A)
6.e Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C54(H54A,H54B,H54C), C54A(H54D,H54E,H54F)
;
_shelx_res_checksum              62242
_olex2_submission_special_instructions 'No special instructions were received'