A Stable Ring-Expanded NHC-Supported Copper Boryl and its Reactivity towards Heterocumulenes
Horsley Downie, Thomas Mardale; Charman, Rex S. C.; Hall, Jonathan W.; Mahon, Mary F.; Lowe, John P.; Liptrot, David Jonathan; Dalton Transactions  (2021) –; doi:10.1039/D1DT03540A

data_7708612
_publ_section_title
;
 A Stable Ring-Expanded NHC-Supported Copper Boryl and its Reactivity
 towards Heterocumulenes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT03540A
_journal_year                    2021
_chemical_formula_moiety         'C45 H73 B Cu N5 O2'
_chemical_formula_sum            'C45 H73 B Cu N5 O2'
_chemical_formula_weight         790.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-10-19 deposited with the CCDC.	2021-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.118(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4621(5)
_cell_length_b                   17.3090(7)
_cell_length_c                   22.5662(11)
_cell_measurement_reflns_used    8736
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      27.2640
_cell_measurement_theta_min      3.4400
_cell_volume                     4477.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0734
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0603
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            42619
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.158
_diffrn_reflns_theta_min         2.949
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77800
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.173
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.523
_exptl_crystal_size_mid          0.395
_exptl_crystal_size_min          0.209
_refine_diff_density_max         1.636
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     534
_refine_ls_number_reflns         11558
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1344
_refine_ls_R_factor_gt           0.0829
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1243P)^2^+5.2203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2219
_refine_ls_wR_factor_ref         0.2552
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7174
_reflns_number_total             11558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03540a2.cif
_cod_data_source_block           e21djl03-cpd8
_cod_database_code               7708612
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.770
_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. Restrained distances
 C35-C34 \\sim C36-C34 \\sim C39-C37 \\sim C38-C37
 with sigma of 0.005
 N4-C34 \\sim N4-C34A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A
 with sigma of 0.02
 N4-C35 \\sim N4-C35A
 with sigma of 0.04
 N4-C36 \\sim N4-C36A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36A
 with sigma of 0.04
 C35-C36 \\sim C36A-C35A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C34 \\sim C35 \\sim C36 \\sim C34A \\sim C36A \\sim C35A: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: C34(0.6) H34(0.6) C35(0.6) H35A(0.6) H35B(0.6) H35C(0.6) C36(0.6)
 H36A(0.6) H36B(0.6) H36C(0.6) C34A(0.4) H34A(0.4) C36A(0.4) H36D(0.4)
 H36E(0.4) H36F(0.4) C35A(0.4) H35D(0.4) H35E(0.4) H35F(0.4)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C31(H31), C34(H34), C37(H37),
 C34A(H34A)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C36A(H36D,H36E,H36F), C35A(H35D,H35E,H35F)
;