Functionalization of Deutero- and Protoporphyrin IX Dimethyl Esters via Palladium-Catalyzed Coupling Reactions.
O'Brien, Jessica M; Sitte, Elisabeth; Flanagan, Keith J.; Kühner, Hannes; Hallen, Lukas J.; Gibbons, Dáire; Senge, Mathias O.; The Journal of organic chemistry 84 (2019) 6158–6173; doi:10.1021/acs.joc.9b00350

data_4033684
_publ_section_title
;
 Functionalization of Deutero- and Protoporphyrin IX Dimethyl Esters via
 Palladium-Catalyzed Coupling Reactions.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6158
_journal_page_last               6173
_journal_paper_doi               10.1021/acs.joc.9b00350
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety
'0.99 (C44 H42 N4 O4), 0.01 (C44 H41 N4 O4 Pd1)'
_chemical_formula_sum            'C44 H41.99 N4 O4 Pd0.01'
_chemical_formula_weight         691.87
_chemical_name_systematic
'3,8-Diphenyl-deuteroporphyrin IX dimethyl ester'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.8161(10)
_cell_length_b                   8.5863(3)
_cell_length_c                   32.5051(12)
_cell_measurement_reflns_used    9746
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.183
_cell_measurement_theta_min      2.506
_cell_volume                     7205.2(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX 3 (Bruker, 2016) '
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.98
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0588
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            89421
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.303
_diffrn_reflns_theta_min         1.481
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              graphite-monochromated
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6604
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0599 before and 0.0525 after correction. The Ratio of minimum to maximum transmission is 0.8856. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             2932
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of chloroform and methanol  by slow evaporation'
_exptl_crystal_size_max          0.556
_exptl_crystal_size_mid          0.268
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         8957
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0873
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0478P)^2^+5.7590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6390
_reflns_number_total             8957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00350_si_001.cif
_cod_data_source_block           kjf179
_cod_database_code               4033684
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.953
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C133-C132 \\sim C1B-C132
 with sigma of 0.02
 C132-C131 \\sim C1C-C131
 with sigma of 0.02
 C133-C132 \\sim C1C-C1B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C133 \\sim C1B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
Uanis(C1B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1A) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(O1)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C132) = Uanis(C1C)
4. Others
 Fixed Sof: H21(0.495) H22(0.5) H23(0.495) H24(0.5) H13A(0.2) H13B(0.2)
 H13C(0.8) H13D(0.8) O1(0.8) O2(0.8) C132(0.2) H13E(0.2) H13F(0.2) C133(0.8)
 C134(0.8) H13G(0.8) H13H(0.8) H13I(0.8) O1A(0.2) O2A(0.2) C1A(0.2) H1AA(0.2)
 H1AB(0.2) H1AC(0.2) C1B(0.2) C1C(0.8) H1CA(0.8) H1CB(0.8) Pd1(0.01)
5.a Secondary CH2 refined with riding coordinates:
 C131(H13A,H13B), C131(H13C,H13D), C171(H17A,H17B), C172(H17C,H17D), C132(H13E,
 H13F), C1C(H1CA,H1CB)
5.b Aromatic/amide H refined with riding coordinates:
 N21(H21), N22(H22), N23(H23), N24(H24), C5(H5), C10(H10), C15(H15), C20(H20),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C82(H82), C83(H83), C84(H84),
  C85(H85), C86(H86)
5.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C71(H71A,H71B,H71C), C121(H12A,H12B,H12C), C174(H17E,
 H17F,H17G), C181(H18A,H18B,H18C), C134(H13G,H13H,H13I), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              7479
_shelx_hkl_checksum              10003
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN micromount with oil'
_olex2_submission_special_instructions 'No special instructions were received'