Reactions of Aluminium(I) with Transition Metal Carbonyls: Scope, Mechanism and Selectivity of CO Homologation
Crimmin, Mark Richard; Kong, Richard Y.; Batuecas, Maria; Chemical Science  (2021) –; doi:10.1039/D1SC04940B

data_1565064
_publ_section_title
;
 &#x000D; Reactions of Aluminium(I) with Transition Metal Carbonyls:
 Scope, Mechanism and Selectivity of CO Homologation&#x000D;
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04940B
_journal_year                    2021
_chemical_formula_moiety
'C66 H82 Al2 Mo N4 O8, 0.13(C7 H8), 0.13(C6 H14)'
_chemical_formula_sum            'C67.62 H84.75 Al2 Mo N4 O8'
_chemical_formula_weight         1231.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-07-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-07-08 deposited with the CCDC.	2021-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.641(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.5349(5)
_cell_length_b                   20.7875(3)
_cell_length_c                   26.1992(5)
_cell_measurement_reflns_used    12708
_cell_measurement_temperature    173.0(3)
_cell_measurement_theta_max      72.9750
_cell_measurement_theta_min      3.6110
_cell_volume                     14342.9(5)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.951
_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     93.00 176.00   1.00   23.77    --  105.13 125.00 120.00   83
  2  \w     73.00 167.00   1.00   23.77    --  105.13  77.00 -90.00   94
  3  \w     75.00 151.00   1.00   23.77    --  105.13 125.00-180.00   76
  4  \w     37.00 133.00   1.00   23.77    --  105.13 -61.00 120.00   96
  5  \w   -110.00 -18.00   1.00    4.36    --  -42.23 -57.00-150.00   92
  6  \w   -117.00 -27.00   1.00    4.36    --  -42.23 -38.00 120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0121851000
_diffrn_orient_matrix_UB_12      -0.0682603000
_diffrn_orient_matrix_UB_13      0.0244189000
_diffrn_orient_matrix_UB_21      -0.0557342000
_diffrn_orient_matrix_UB_22      -0.0084290000
_diffrn_orient_matrix_UB_23      -0.0066993000
_diffrn_orient_matrix_UB_31      -0.0130971000
_diffrn_orient_matrix_UB_32      -0.0274995000
_diffrn_orient_matrix_UB_33      -0.0584618000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0551
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            27591
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.656
_diffrn_reflns_theta_min         3.356
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.136
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78751
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.141
_exptl_crystal_description       block
_exptl_crystal_F_000             5204
_exptl_crystal_size_max          0.443
_exptl_crystal_size_mid          0.385
_exptl_crystal_size_min          0.129
_refine_diff_density_max         1.939
_refine_diff_density_min         -1.095
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.940
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1540
_refine_ls_number_reflns         27591
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      0.942
_refine_ls_R_factor_all          0.1099
_refine_ls_R_factor_gt           0.0702
_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^)+(0.1489P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1922
_refine_ls_wR_factor_ref         0.2193
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16366
_reflns_number_total             27591
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           3-Mo
_cod_original_cell_volume        14342.9(4)
_cod_database_code               1565064
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C66 H82 N4 O8 Al2 Mo'
_chemical_oxdiff_usercomment     RK560
_reflns_odcompleteness_completeness 98.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.372(13)
 0.628(13)
2. 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
3. Restrained distances
 C73-C80
 1.5 with sigma of 0.02
 C67-C68 = C68-C69 = C69-C70 = C70-C71 = C71-C72
 1.55 with sigma of 0.02
 C67-C69 = C68-C70 = C69-C71 = C70-C72
 2.26 with sigma of 0.02
 C78-C80 \\sim C80-C74
 with sigma of 0.01
4. Restrained planarity
 C80, C76, H76, C77, C75, H77, C78, C74, H75, H78, C73
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C73 \\sim C76 \\sim C77 \\sim C75 \\sim C78 \\sim C74 \\sim C80: within 4A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C69 \\sim C72 \\sim C71 \\sim C70 \\sim C68 \\sim C67: within 8A with sigma of
0.1 and sigma for terminal atoms of 0.1
6. Others
 Fixed Sof: C76(0.25) H76(0.25) C77(0.25) H77(0.25) C78(0.25) H78(0.25)
 C73(0.25) C74(0.25) H74(0.25) C75(0.25) H75(0.25) C80(0.25) H80A(0.25)
 H80B(0.25) H80C(0.25) C72(0.25) H72A(0.25) H72B(0.25) H72C(0.25) C70(0.25)
 H70A(0.25) H70B(0.25) C68(0.25) H68A(0.25) H68B(0.25) C69(0.25) H69A(0.25)
 H69B(0.25) C67(0.25) H67A(0.25) H67B(0.25) H67C(0.25) C71(0.25) H71A(0.25)
 H71B(0.25)
7.a Ternary CH refined with riding coordinates:
 C64B(H64B), C29A(H29A), C29B(H29B), C46B(H46B), C64A(H64A), C61A(H61A),
 C58A(H58A), C61B(H61B), C20A(H20A), C32B(H32B), C46A(H46A), C32A(H32A),
 C49A(H49A), C58B(H58B), C49B(H49B), C20B(H20B)
7.b Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C68(H68A,H68B), C69(H69A,H69B), C71(H71A,H71B)
7.c Me refined with riding coordinates:
 C80(H80A,H80B,H80C), C72(H72A,H72B,H72C), C67(H67A,H67B,H67C)
7.d Aromatic/amide H refined with riding coordinates:
 C44B(H44B), C37B(H37B), C27B(H27B), C56A(H56A), C42B(H42B), C18A(H18A),
 C11B(H11B), C11A(H11A), C17A(H17A), C37A(H37A), C43B(H43B), C26A(H26A),
 C55A(H55A), C54A(H54A), C42A(H42A), C25B(H25B), C27A(H27A), C25A(H25A),
 C26B(H26B), C44A(H44A), C43A(H43A), C56B(H56B), C18B(H18B), C16B(H16B),
 C55B(H55B), C17B(H17B), C16A(H16A), C54B(H54B), C76(H76), C77(H77), C78(H78),
 C74(H74), C75(H75)
7.e Fitted hexagon refined as free rotating group:
 C76(C77,C78,C73,C74,C75)
7.f Idealised Me refined as rotating group:
 C9A(H9AA,H9AB,H9AC), C65A(H65D,H65E,H65F), C39A(H39D,H39E,H39F), C65B(H65A,
 H65B,H65C), C35B(H35A,H35B,H35C), C30A(H30D,H30E,H30F), C47A(H47D,H47E,H47F),
 C9B(H9BA,H9BB,H9BC), C13B(H13A,H13B,H13C), C47B(H47A,H47B,H47C), C63B(H63A,
 H63B,H63C), C66A(H66D,H66E,H66F), C48B(H48A,H48B,H48C), C66B(H66A,H66B,H66C),
 C13A(H13D,H13E,H13F), C35A(H35D,H35E,H35F), C48A(H48D,H48E,H48F), C39B(H39A,
 H39B,H39C), C60A(H60D,H60E,H60F), C51B(H51A,H51B,H51C), C60B(H60A,H60B,H60C),
 C34A(H34D,H34E,H34F), C33A(H33D,H33E,H33F), C30B(H30A,H30B,H30C), C22A(H22D,
 H22E,H22F), C63A(H63D,H63E,H63F), C34B(H34A,H34B,H34C), C59A(H59D,H59E,H59F),
 C21A(H21D,H21E,H21F), C33B(H33A,H33B,H33C), C21B(H21A,H21B,H21C), C31A(H31D,
 H31E,H31F), C62A(H62D,H62E,H62F), C22B(H22A,H22B,H22C), C51A(H51D,H51E,H51F),
 C59B(H59A,H59B,H59C), C62B(H62A,H62B,H62C), C50B(H50A,H50B,H50C), C31B(H31A,
 H31B,H31C), C50A(H50D,H50E,H50F)
;
_shelx_res_checksum              42500
_shelx_hkl_checksum              65405
_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 1.345
_oxdiff_exptl_absorpt_empirical_full_min 0.810