Alkyne insertion into Cu–Al bonds and selective functionalization to form copper acyl compounds
McManus, Caitilín; Crumpton, Agamemnon E.; Aldridge, Simon; Chemical Communications  (2022) –; doi:10.1039/D2CC02578G

data_7130330
_publ_section_title
;
 Alkyne insertion into Cu--Al bonds and selective functionalization to
 form copper acyl compounds
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC02578G
_journal_year                    2022
_chemical_formula_moiety         'C65 H99 Al Cu N2 O P, 2(C7 H8)'
_chemical_formula_sum            'C79 H115 Al Cu N2 O P'
_chemical_formula_weight         1230.21
_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     dual
_audit_creation_date             2021-07-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-03-11 deposited with the CCDC.	2022-06-22 downloaded from the CCDC.
;
_cell_angle_alpha                75.776(3)
_cell_angle_beta                 78.631(3)
_cell_angle_gamma                84.115(3)
_cell_formula_units_Z            2
_cell_length_a                   12.6157(4)
_cell_length_b                   15.1843(5)
_cell_length_c                   20.1243(7)
_cell_measurement_reflns_used    11475
_cell_measurement_temperature    150.03(18)
_cell_measurement_theta_max      76.0940
_cell_measurement_theta_min      3.5640
_cell_volume                     3657.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.03(18)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -39.00  -8.00   1.00    5.00    --  -42.78  57.00-180.00   31
  2  \w      1.00  33.00   1.00    5.00    --  -42.78  19.00-150.00   32
  3  \w     -5.00  36.00   1.00    5.00    --  -42.78  19.00 120.00   41
  4  \w      5.00  36.00   1.00    5.00    --  -42.78  19.00-180.00   31
  5  \w     -5.00  29.00   1.00    5.00    --  -42.78  19.00-120.00   34
  6  \w      2.00  31.00   1.00    5.00    --  -42.78  19.00 -90.00   29
  7  \w     -5.00  33.00   1.00    5.00    --  -42.78  19.00 -30.00   38
  8  \w    -22.00  14.00   1.00    5.00    --  -42.78  38.00  90.00   36
  9  \w     66.00 116.00   1.00    5.00    --   42.78 178.00   0.00   50
 10  \w     61.00 121.00   1.00    5.00    --   42.78-178.00 120.00   60
 11  \w     94.00 130.00   1.00    5.00    --   42.78 178.00 -90.00   36
 12  \w     40.00  65.00   1.00   15.00    --  111.00 -45.00-180.00   25
 13  \w     43.00  83.00   1.00   15.00    --  111.00 -61.00  90.00   40
 14  \w     39.00  88.00   1.00   15.00    --  111.00 -95.00 120.00   49
 15  \w     40.00  68.00   1.00   15.00    --  111.00 -45.00 150.00   28
 16  \w     88.00 135.00   1.00   15.00    --  111.00  45.00-150.00   47
 17  \w     65.00 106.00   1.00   15.00    --  111.00-124.00  20.00   41
 18  \w     76.00 177.00   1.00   15.00    --  111.00  15.00 150.00  101
 19  \w     63.00  95.00   1.00   15.00    --  111.00-125.00   0.00   32
 20  \w     54.00  91.00   1.00   15.00    --  111.00 -61.00 120.00   37
 21  \w     42.00  93.00   1.00   15.00    --  111.00 -61.00 -30.00   51
 22  \w    132.00 159.00   1.00   15.00    --  111.00 125.00  30.00   27
 23  \w     45.00  70.00   1.00   15.00    --  111.00-125.00 -60.00   25
 24  \w    127.00 160.00   1.00   15.00    --  111.00  30.00-180.00   33
 25  \w     52.00  77.00   1.00   15.00    --  111.00 -61.00-180.00   25
 26  \w     54.00  90.00   1.00   15.00    --  111.00 -61.00 -90.00   36
 27  \w     78.00 105.00   1.00   15.00    --  111.00 -95.00-180.00   27
 28  \w     66.00 106.00   1.00   15.00    --  111.00 -95.00   0.00   40
 29  \w     44.00  93.00   1.00   15.00    --  111.00 -61.00  30.00   49
 30  \w    139.00 178.00   1.00   15.00    --  111.00  61.00  90.00   39
 31  \w     92.00 120.00   1.00   15.00    --  111.00  30.00-180.00   28
 32  \w    134.00 161.00   1.00   15.00    --  111.00  45.00   0.00   27
 33  \w     41.00  67.00   1.00   15.00    --  111.00 -45.00  30.00   26
 34  \w     88.00 127.00   1.00   15.00    --  111.00  45.00   0.00   39
 35  \w     44.00 112.00   1.00   15.00    --  111.00-125.00 -30.00   68
 36  \w     42.00  70.00   1.00   15.00    --  111.00-125.00-150.00   28
 37  \w     86.00 112.00   1.00   15.00    --  111.00-125.00-150.00   26
 38  \w     90.00 174.00   1.00   15.00    --  111.00  45.00  60.00   84
 39  \w    106.00 169.00   1.00   15.00    --  111.00 125.00   0.00   63
 40  \w     82.00 109.00   1.00   15.00    --  111.00-125.00 -60.00   27
 41  \w     40.00  65.00   1.00   15.00    --  111.00 -45.00  90.00   25
 42  \w    101.00 129.00   1.00   15.00    --  111.00-148.00-143.00   28
 43  \w     98.00 147.00   1.00   15.00    --  111.00  45.00  30.00   49
 44  \w     61.00 107.00   1.00   15.00    --  111.00-101.00-140.37   46
 45  \w     70.00 108.00   1.00   15.00    --  111.00-125.00  90.00   38
 46  \w     82.00 107.00   1.00   15.00    --  111.00 -97.00  60.68   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0121777000
_diffrn_orient_matrix_UB_12      -0.0759811000
_diffrn_orient_matrix_UB_13      -0.0399860000
_diffrn_orient_matrix_UB_21      0.0302033000
_diffrn_orient_matrix_UB_22      0.0704027000
_diffrn_orient_matrix_UB_23      -0.0692769000
_diffrn_orient_matrix_UB_31      0.1204353000
_diffrn_orient_matrix_UB_32      -0.0161548000
_diffrn_orient_matrix_UB_33      0.0065917000
_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  0.0477
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41026
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.199
_diffrn_reflns_theta_min         3.007
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.061
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85314
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.117
_exptl_crystal_description       plate
_exptl_crystal_F_000             1336
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.813
_refine_diff_density_min         -0.636
_refine_diff_density_rms         0.082
_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     795
_refine_ls_number_reflns         15110
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0630
_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^)+(0.1097P)^2^+1.6986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1713
_refine_ls_wR_factor_ref         0.1889
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11803
_reflns_number_total             15110
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02578g2.cif
_cod_data_source_block           2-Et
_cod_database_code               7130330
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C60 H70 Al1 P1 O1 N2 Cu1'
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.676
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Uiso/Uaniso restraints and constraints
C49 \\sim C50 \\sim C48: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C53 \\sim C55 \\sim C56: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C205 \\sim C206: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C48 \\sim C49: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
3. Rigid body (RIGU) restrains
 C50, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C32(H32), C44(H44), C41(H41), C29(H29)
4.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C51(H51A,H51B)
4.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C11(H11), C4(H4), C2(H2), C39(H39), C38(H38), C25(H25), C37(H37),
 C27(H27), C26(H26), C204(H204), C203(H203), C202(H202), C201(H201), C200(H200),
  C104(H104), C100(H100), C101(H101), C103(H103), C102(H102)
4.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C34(H34A,H34B,H34C), C30(H30A,H30B,H30C),
 C22(H22A,H22B,H22C), C43(H43A,H43B,H43C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C47(H47A,H47B,H47C), C33(H33A,H33B,H33C), C42(H42A,H42B,H42C), C45(H45A,
 H45B,H45C), C21(H21A,H21B,H21C), C46(H46A,H46B,H46C), C17(H17A,H17B,H17C),
 C52(H52A,H52B,H52C), C31(H31A,H31B,H31C), C20(H20A,H20B,H20C), C55(H55A,H55B,
 H55C), C59(H59A,H59B,H59C), C58(H58A,H58B,H58C), C64(H64A,H64B,H64C), C62(H62A,
 H62B,H62C), C63(H63A,H63B,H63C), C60(H60A,H60B,H60C), C54(H54A,H54B,H54C),
 C206(H20D,H20E,H20F), C106(H10A,H10B,H10C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              6825
_shelx_hkl_checksum              8015
_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 1.450
_oxdiff_exptl_absorpt_empirical_full_min 0.728