The electrosynthesis of highly encumbered biaryls from aryl <i>o</i>-iodobenzyl ethers by a radical to polar crossover sequence.
Pearce, James E.; Hodgson, Jack; Folgueiras-Amador, Ana A; Fish, Johanna A.; Carroll, Robert C.; Coles, Simon J.; Parsons, Philip J.; Brown, Richard C. D.; Harrowven, David C.; Chemical communications (Cambridge, England) 61 (2025) 4042–4045; doi:10.1039/d4cc06061j

data_7134209
_publ_section_title
;
 The electrosynthesis of highly encumbered biaryls from aryl
 <i>o</i>-iodobenzyl ethers by a radical to polar crossover sequence.
;
_journal_issue                   20
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4042
_journal_page_last               4045
_journal_paper_doi               10.1039/d4cc06061j
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C37.134 H26.267 I6 N12 Zn3, 0.143(C16 H18 O)'
_chemical_formula_sum            'C39.42 H28.84 I6 N12 O0.14 Zn3'
_chemical_formula_weight         1630.36
_chemical_name_common            BBA-10-Me
_chemical_name_systematic
'(2',4',6'-trimethyl-[1,1'-biphenyl]-2-yl)methanol absorbed in crystalline sponge'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-18
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-18 deposited with the CCDC.	2025-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.5130(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.0015(5)
_cell_length_b                   14.89120(10)
_cell_length_c                   31.1462(4)
_cell_measurement_reflns_used    17197
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.1670
_cell_measurement_theta_min      2.5560
_cell_volume                     15907.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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   -174.00 -89.00   0.50    4.00    -- -103.00 -33.00  18.00  170
  2  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00 -60.00   78
  3  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00 150.00   78
  4  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00   0.00   78
  5  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00-180.00   78
  6  \w   -104.00 -30.00   0.50    4.00    -- -103.00  77.00 -90.00  148
  7  \w   -104.00 -30.00   0.50    4.00    -- -103.00  77.00 150.00  148
  8  \w   -104.00 -30.00   0.50    4.00    -- -103.00  77.00 120.00  148
  9  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00  30.00   78
 10  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00 -90.00   78
 11  \w    -69.00 -30.00   0.50    4.00    -- -103.00  61.00 -30.00   78
 12  \w     88.00 175.00   0.50    4.00    --  101.75  33.00 176.00  174
 13  \w     29.00  73.00   0.50    4.00    --  101.75 -61.00   0.00   88
 14  \w     29.00  73.00   0.50    4.00    --  101.75 -61.00  30.00   88
 15  \w     29.00 106.00   0.50    4.00    --  101.75 -94.00-150.00  154
 16  \w     29.00  73.00   0.50    4.00    --  101.75 -61.00  60.00   88
 17  \w     29.00 108.00   0.50    4.00    --  101.75 -77.00-150.00  158
 18  \w    -36.00  27.00   0.50    0.75    --  -46.47  33.00 176.00  126
 19  \w   -120.00 -33.00   0.50    0.75    --  -46.47 -33.00  18.00  174
 20  \w     34.00 120.00   0.50    0.75    --   46.47  33.00 176.00  172
 21  \w    -27.00  40.00   0.50    0.75    --   46.47 -33.00  18.00  134
 22  \w    -24.00  29.00   0.50    0.75    --  -46.47  19.00-120.00  106
 23  \w    -28.00  28.00   0.50    0.75    --   46.47 -19.00-120.00  112
 24  \w     32.00 118.00   0.50    0.75    --   46.47  57.00 -90.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details
'Rigaku Oxford Difffraction, UG2 \k goniometer'
_diffrn_measurement_device_type
'Rigaku 007HF equipped with Varimax confocal mirrors and a UG2 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen loops'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0183112000
_diffrn_orient_matrix_UB_12      -0.0058079000
_diffrn_orient_matrix_UB_13      0.0491857000
_diffrn_orient_matrix_UB_21      -0.0367284000
_diffrn_orient_matrix_UB_22      0.0436137000
_diffrn_orient_matrix_UB_23      0.0111432000
_diffrn_orient_matrix_UB_31      -0.0182565000
_diffrn_orient_matrix_UB_32      -0.0936358000
_diffrn_orient_matrix_UB_33      0.0021264000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'Varimax focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            73063
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.249
_diffrn_reflns_theta_min         2.577
_diffrn_source                   'Rotating anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku 007 HF'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    19.551
_exptl_absorpt_correction_T_max  0.405
_exptl_absorpt_correction_T_min  0.138
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       block
_exptl_crystal_F_000             6068
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.526
_refine_diff_density_min         -0.867
_refine_diff_density_rms         0.216
_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     803
_refine_ls_number_reflns         14520
_refine_ls_number_restraints     390
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0637
_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^)+(0.1629P)^2^+10.5469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2135
_refine_ls_wR_factor_ref         0.2250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11715
_reflns_number_total             14520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06061j2.cif
_cod_data_source_block           BBA_10_Me_CrystallineSponge
_cod_depositor_comments
'Adding full bibliography for 7134208--7134209.cif.'
_cod_database_code               7134209
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         '(Zn3 I6 N12 H24 C36) (C16 H18 O)2 (C6 H12)3'
_chemical_oxdiff_usercomment     JP-9300-15
_shelx_estimated_absorpt_t_max   0.387
_shelx_estimated_absorpt_t_min   0.111
_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, All O(H) groups
2. Restrained distances
 O1-C13
 1.43 with sigma of 0.02
 C13-C5
 1.5 with sigma of 0.01
 C12-C15 = C10-C16 = C4-C7
 1.5 with sigma of 0.02
 C802-C801 = C802-C803 = C801-C806 = C806-C805 = C805-C804 = C804-C803
 1.54 with sigma of 0.02
 C4-C13 = C6-C13
 2.4 with sigma of 0.04
 C802-C806 = C802-C804 = C801-C805 = C806-C804 = C805-C803
 2.54 with sigma of 0.04
 C7-C14 \\sim C14-C9
 with sigma of 0.02
 I306-Zn33 \\sim I406-Zn43
 with sigma of 0.02
 C5-C7 \\sim C7-C3
 with sigma of 0.04
 C7-C15 \\sim C15-C11
 with sigma of 0.04
 C8-C4 \\sim C4-C12
 with sigma of 0.04
 C11-C16 \\sim C16-C9
 with sigma of 0.04
 C8-C1 \\sim C1-C12
 with sigma of 0.04
 I305-N306 \\sim I405-N306
 with sigma of 0.04
 I305-Zn33 \\sim I405-Zn43
 with sigma of 0.02
 Zn33-N307 \\sim Zn43-N307
 with sigma of 0.02
 Zn33-N306 \\sim Zn43-N306
 with sigma of 0.02
 I305-N307 \\sim I405-N307
 with sigma of 0.04
 I306-I305 \\sim I406-I405
 with sigma of 0.04
 I306-N307 \\sim I406-N307
 with sigma of 0.04
 I306-N306 \\sim I406-N306
 with sigma of 0.04
 I401-N301 \\sim I301-N301
 with sigma of 0.04
 I402-I401 \\sim I302-I301
 with sigma of 0.04
 I402-Zn41 \\sim I302-Zn31
 with sigma of 0.02
 I402-N301 \\sim I302-N301
 with sigma of 0.04
 I401-Zn41 \\sim I301-Zn31
 with sigma of 0.02
 Zn41-N301 \\sim Zn31-N301
 with sigma of 0.02
 I303-N305 \\sim I403-N305
 with sigma of 0.04
 I303-I304 \\sim I403-I404
 with sigma of 0.04
 I304-N305 \\sim I404-N305
 with sigma of 0.04
 I303-Zn32 \\sim I403-Zn42
 with sigma of 0.02
 I304-Zn32 \\sim I404-Zn42
 with sigma of 0.02
 Zn32-N305 \\sim Zn42-N305
 with sigma of 0.02
 I404-Zn42 \\sim I504-Zn52
 with sigma of 0.02
 I403-Zn42 \\sim I503-Zn52
 with sigma of 0.02
 C802-C804 \\sim C806-C804 \\sim C801-C803 \\sim C801-C805 \\sim C805-C803
\\sim C802-C806
 with sigma of 0.04
 C802-C801 \\sim C801-C806 \\sim C806-C805 \\sim C805-C804 \\sim C804-C803
\\sim C803-C802
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C13 \\sim C14 \\sim C8 \\sim C7 \\sim C9 \\sim C12 \\sim C4 \\sim C10 \\sim C11
\\sim C15 \\sim C5 \\sim C3 \\sim C16 \\sim C6 \\sim C2 \\sim C1 \\sim O1:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C802 \\sim C801 \\sim C806 \\sim C805 \\sim C804 \\sim C803: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C13, C14, C8, C7, C9, C12, C4, C10, C11, C15, C5, C3, C16, C6, C2, C1, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C802, C801, C806, C805, C804, C803
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(I306)+Sof(I305)+Sof(Zn33)]+1*[Sof(I406)+Sof(Zn43)+Sof(I405)]+1*
 [Sof(I506)+Sof(I505)+Sof(Zn53)]=1 with esd of 0.00001
 1*[Sof(I303)+Sof(I304)+Sof(Zn32)]+1*[Sof(I403)+Sof(Zn42)+Sof(I404)]+1*
 [Sof(I503)+Sof(I504)+Sof(Zn52)]=1 with esd of 0.00001
 Sof(I301)=Sof(Zn31)=Sof(I302)=1-FVAR(1)
 Sof(I402)=Sof(I401)=Sof(Zn41)=FVAR(1)
 Sof(I306)=Sof(I305)=Sof(Zn33)=FVAR(2)
 Sof(I406)=Sof(Zn43)=Sof(I405)=FVAR(3)
 Sof(I506)=Sof(I505)=Sof(Zn53)=FVAR(4)
 Sof(I303)=Sof(I304)=Sof(Zn32)=FVAR(5)
 Sof(I403)=Sof(Zn42)=Sof(I404)=FVAR(6)
 Sof(I503)=Sof(I504)=Sof(Zn52)=FVAR(7)
 Fixed Sof: C802(0.18893) H80A(0.18893) H80B(0.18893) C801(0.18893)
 H80C(0.18893) H80D(0.18893) C806(0.18893) H80E(0.18893) H80F(0.18893)
 C805(0.18893) H80G(0.18893) H80H(0.18893) C804(0.18893) H80I(0.18893)
 H80J(0.18893) C803(0.18893) H80K(0.18893) H80L(0.18893) C14(0.1427)
 H14A(0.1427) H14B(0.1427) H14C(0.1427) C4(0.1427) C5(0.1427) C6(0.1427)
 H6(0.1427) C1(0.1427) H1(0.1427) C2(0.1427) H2(0.1427) C3(0.1427) H3(0.1427)
 C7(0.1427) C8(0.1427) C9(0.1427) H9(0.1427) C10(0.1427) C11(0.1427)
 H11(0.1427) C12(0.1427) O1(0.1427) H1A(0.1427) C15(0.1427) H15A(0.1427)
 H15B(0.1427) H15C(0.1427) C16(0.1427) H16A(0.1427) H16B(0.1427) H16C(0.1427)
 C13(0.1427) H13A(0.1427) H13B(0.1427)
 Fixed Uiso: H311(0.08) I506(0.08) I505(0.08) Zn53(0.08) I503(0.08) I504(0.08)
 Zn52(0.08)
6.a Secondary CH2 refined with riding coordinates:
 C802(H80A,H80B), C801(H80C,H80D), C806(H80E,H80F), C805(H80G,H80H), C804(H80I,
 H80J), C803(H80K,H80L), C13(H13A,H13B)
6.b Aromatic/amide H refined with riding coordinates:
 C304(H304), C305(H305), C329(H329), C328(H328), C320(H320), C319(H319),
 C314(H314), C315(H315), C322(H322), C335(H335), C333(H333), C310(H310),
 C332(H332), C323(H323), C336(H336), C331(H331), C330(H330), C311(H311),
 C301(H301), C302(H302), C312(H312), C317(H317), C313(H313), C318(H318), C6(H6),
  C1(H1), C2(H2), C3(H3), C9(H9), C11(H11)
6.c Fitted hexagon refined as free rotating group:
 C4(C5,C6,C1,C2,C3), C7(C8,C9,C10,C11,C12)
6.d Tetrahedral OH refined with riding coordinates:
 O1(H1A)
6.e Idealised Me refined with everything fixed:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              99922
_shelx_hkl_checksum              58368
_olex2_date_sample_data_collection 2022-11-24
_olex2_date_sample_submission    2022-11-24
_olex2_submission_original_sample_id BBA-10-Me
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.689
_oxdiff_exptl_absorpt_empirical_full_min 0.450