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_1565065
_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         'C70 H89 Al2 Mn N4 O6, 2(C7 H8)'
_chemical_formula_sum            'C84 H105 Al2 Mn N4 O6'
_chemical_formula_weight         1375.61
_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     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                 91.256(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.8869(7)
_cell_length_b                   22.7289(9)
_cell_length_c                   19.8568(9)
_cell_measurement_reflns_used    5622
_cell_measurement_temperature    173.1(2)
_cell_measurement_theta_max      72.5360
_cell_measurement_theta_min      3.8560
_cell_volume                     7619.6(6)
_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      173.1(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.972
_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   -111.00 -19.00   1.00    8.89    --  -42.36 -57.00-120.00   92
  2  \w   -117.00 -32.00   1.00    8.89    --  -42.36 -38.00 150.00   85
  3  \w     50.00 134.00   1.00   55.34    --  105.13 -61.00 150.00   84
  4  \w     52.00 134.00   1.00   55.34    --  105.13 -61.00 -30.00   82
  5  \w     24.00 109.00   1.00   55.34    --  105.13 -95.00   0.00   85
  6  \w     78.00 170.00   1.00   55.34    --  105.13  77.00 -60.00   92
;
_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      0.0525101000
_diffrn_orient_matrix_UB_12      -0.0470315000
_diffrn_orient_matrix_UB_13      0.0344947000
_diffrn_orient_matrix_UB_21      -0.0740666000
_diffrn_orient_matrix_UB_22      -0.0373707000
_diffrn_orient_matrix_UB_23      0.0137179000
_diffrn_orient_matrix_UB_31      0.0095305000
_diffrn_orient_matrix_UB_32      -0.0313577000
_diffrn_orient_matrix_UB_33      -0.0681268000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.1096
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24570
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.668
_diffrn_reflns_theta_min         3.261
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.057
_exptl_absorpt_correction_T_max  0.827
_exptl_absorpt_correction_T_min  0.697
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_description       block
_exptl_crystal_F_000             2944
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.139
_refine_diff_density_max         0.983
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.864
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     909
_refine_ls_number_reflns         24570
_refine_ls_number_restraints     197
_refine_ls_restrained_S_all      0.867
_refine_ls_R_factor_all          0.1357
_refine_ls_R_factor_gt           0.0752
_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^)+(0.1275P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1923
_refine_ls_wR_factor_ref         0.2248
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11769
_reflns_number_total             24570
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           4-Mn
_cod_original_cell_volume        7619.7(6)
_cod_database_code               1565065
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C70 H89 Al2 Mn N4 O6'
_chemical_oxdiff_usercomment     RK548
_reflns_odcompleteness_completeness 98.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7524(10)
 0.2476(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C70'-C76'
 1.5 with sigma of 0.02
 C71'-C76' \\sim C76'-C75'
 with sigma of 0.02
4. Restrained planarity
 C83', C81', C82', C77', C78', C79', C80'
 with sigma of 0.1
 C72', C71', C70', C75', C74', C73', C76'
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C81 \\sim C80 \\sim C79 \\sim C78 \\sim C77 \\sim C82 \\sim C83 \\sim C83'
\\sim C81' \\sim C80' \\sim C82' \\sim C79' \\sim C77' \\sim C78': within 1A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C70 \\sim C71 \\sim C76 \\sim C72'
\\sim C73' \\sim C71' \\sim C74' \\sim C70' \\sim C75' \\sim C76': within 1.5A
with sigma of 0.01 and sigma for terminal atoms of 0.01
6. Others
 Sof(C83')=Sof(H76')=Sof(H0AA)=Sof(H8AA)=Sof(C81')=Sof(H72')=Sof(C82')=
 Sof(H71')=Sof(C77')=Sof(C78')=Sof(H75')=Sof(C79')=Sof(H74')=Sof(C80')=
 Sof(H73')=1-FVAR(1)
 Sof(C81)=Sof(H81)=Sof(C80)=Sof(H80)=Sof(C79)=Sof(H79)=Sof(C78)=Sof(H78)=
 Sof(C77)=Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=FVAR(1)
 Sof(C72')=Sof(H81')=Sof(C71')=Sof(H82')=Sof(C70')=Sof(C75')=Sof(H78')=
 Sof(C74')=Sof(H79')=Sof(C73')=Sof(H80')=Sof(C76')=Sof(H83')=Sof(H9AA)=
 Sof(H0BA)=1-FVAR(2)
 Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75)=
 Sof(C70)=Sof(C71)=Sof(H71)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C56(H56), C53(H53), C24(H24), C27(H27), C39(H39), C36(H36), C65(H65), C68(H68)
7.b Me refined with riding coordinates:
 C17(H17A,H17B,H17C)
7.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C44(H44), C61(H61), C49(H49), C62(H62), C32(H32), C50(H50),
 C34(H34), C51(H51), C33(H33), C22(H22), C63(H63), C20(H20), C21(H21), C72(H72),
  C73(H73), C74(H74), C75(H75), C71(H71), C81(H81), C80(H80), C79(H79),
 C78(H78), C82(H82), C8(H8), C11(H11), C10(H10), C9(H9), C81'(H72'), C82'(H71'),
  C78'(H75'), C79'(H74'), C80'(H73'), C72'(H81'), C71'(H82'), C75'(H78'),
 C74'(H79'), C73'(H80')
7.d Fitted hexagon refined as free rotating group:
 C72(C73,C74,C75,C70,C71), C81(C80,C79,C78,C77,C82), C81'(C82',C77',C78',C79',
 C80'), C72'(C71',C70',C75',C74',C73')
7.e Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C46(H46A,H46B,H46C), C55(H55A,H55B,H55C), C54(H54A,H54B,
 H54C), C13(H13A,H13B,H13C), C58(H58A,H58B,H58C), C28(H28A,H28B,H28C), C37(H37A,
 H37B,H37C), C57(H57A,H57B,H57C), C67(H67A,H67B,H67C), C25(H25A,H25B,H25C),
 C26(H26A,H26B,H26C), C66(H66A,H66B,H66C), C3AA(H3AA,H3AB,H3AC), C41(H41A,H41B,
 H41C), C40(H40A,H40B,H40C), C29(H29A,H29B,H29C), C38(H38A,H38B,H38C), C69(H69A,
 H69B,H69C), C83(H83A,H83B,H83C), C12(H12A,H12B,H12C), C76(H76A,H76B,H76C),
 C83'(H76',H0AA,H8AA), C76'(H83',H9AA,H0BA)
;
_shelx_res_checksum              36379
_shelx_hkl_checksum              83670
_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 1.287
_oxdiff_exptl_absorpt_empirical_full_min 0.775