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_1565069
_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         'C69 H88 Al2 Mn N4 O5, C7 H8'
_chemical_formula_sum            'C76 H96 Al2 Mn N4 O5'
_chemical_formula_weight         1254.46
_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
_audit_creation_date             2019-02-21
_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                 90.526(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.8912(5)
_cell_length_b                   20.7695(8)
_cell_length_c                   19.8211(8)
_cell_measurement_reflns_used    6930
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      28.1030
_cell_measurement_theta_min      2.5770
_cell_volume                     6953.4(4)
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0382
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.809
_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    -11.00  52.00   1.00  162.69    --  -13.18  77.00   0.00   63
  2  \w      4.00  51.00   1.00  162.69    --   14.27  77.00 120.00   47
  3  \w    -78.00 -52.00   1.00  162.69    --  -13.02 -77.00-120.00   26
  4  \w    -16.00  10.00   1.00  162.69    --  -13.02 -77.00-120.00   26
  5  \w     24.00  53.00   1.00  162.69    --   14.12 -99.00 -30.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0234114000
_diffrn_orient_matrix_UB_12      0.0047636000
_diffrn_orient_matrix_UB_13      0.0294710000
_diffrn_orient_matrix_UB_21      -0.0032417000
_diffrn_orient_matrix_UB_22      0.0338561000
_diffrn_orient_matrix_UB_23      -0.0041415000
_diffrn_orient_matrix_UB_31      -0.0346864000
_diffrn_orient_matrix_UB_32      -0.0000348000
_diffrn_orient_matrix_UB_33      0.0198346000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0840
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.809
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27739
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.809
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.307
_diffrn_reflns_theta_min         2.412
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.268
_exptl_absorpt_correction_T_max  0.970
_exptl_absorpt_correction_T_min  0.953
_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    1.198
_exptl_crystal_description       block
_exptl_crystal_F_000             2684
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.176
_refine_diff_density_max         1.108
_refine_diff_density_min         -0.682
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     844
_refine_ls_number_reflns         14003
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1176
_refine_ls_R_factor_gt           0.0765
_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^)+(0.0957P)^2^+6.9693P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1917
_refine_ls_wR_factor_ref         0.2194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9373
_reflns_number_total             14003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           3-Mn
_cod_database_code               1565069
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C69 H69 N4 O5 Al2 Mn'
_chemical_oxdiff_usercomment     RK236
_reflns_odcompleteness_completeness 99.26
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C175-C176 \\sim C176-C171
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C70 \\sim C75 \\sim C73 \\sim C76 \\sim C71 \\sim C74 \\sim C72 \\sim C176
\\sim C170 \\sim C175 \\sim C171 \\sim C174 \\sim C172 \\sim C173: within 1A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C25 \\sim C24: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
C53 \\sim C153 \\sim C54 \\sim C154: within 1A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C55 \\sim C56 \\sim C57: within 1A with sigma of 0.01 and sigma for terminal
atoms of 0.01
4. Others
 Sof(C176)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C170)=Sof(C171)=Sof(H171)=
 Sof(C172)=Sof(H172)=Sof(C173)=Sof(H173)=Sof(C174)=Sof(H174)=Sof(C175)=
 Sof(H175)=1-FVAR(1)
 Sof(C70)=Sof(C75)=Sof(H75)=Sof(C73)=Sof(H73)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 Sof(H76C)=Sof(C71)=Sof(H71)=Sof(C74)=Sof(H74)=Sof(C72)=Sof(H72)=FVAR(1)
 Sof(C153)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C154)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=1-FVAR(2)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C38(H38), C67(H67), C26(H26), C23(H23), C55(H55), C64(H64), C35(H35)
5.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C60(H60), C31(H31), C33(H33), C61(H61), C32(H32), C62(H62),
 C14(H14), C21(H21), C19(H19), C43(H43), C7(H7), C50(H50), C49(H49), C8(H8),
 C48(H48), C10(H10), C9(H9), C75(H75), C73(H73), C71(H71), C74(H74), C72(H72),
 C171(H171), C172(H172), C173(H173), C174(H174), C175(H175)
5.c Fitted hexagon refined as free rotating group:
 C170(C171,C172,C173,C174,C175)
5.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C16(H16A,H16B,H16C), C28(H28A,H28B,H28C), C12(H12A,H12B,
 H12C), C39(H39A,H39B,H39C), C36(H36A,H36B,H36C), C69(H69A,H69B,H69C), C37(H37A,
 H37B,H37C), C27(H27A,H27B,H27C), C68(H68A,H68B,H68C), C65(H65A,H65B,H65C),
 C66(H66A,H66B,H66C), C40(H40A,H40B,H40C), C56(H56A,H56B,H56C), C25(H25A,H25B,
 H25C), C57(H57A,H57B,H57C), C54(H54A,H54B,H54C), C24(H24A,H24B,H24C), C11(H11A,
 H11B,H11C), C53(H53A,H53B,H53C), C76(H76A,H76B,H76C), C176(H17A,H17B,H17C),
 C45(H45A,H45B,H45C), C153(H15A,H15B,H15C), C154(H15D,H15E,H15F)
;
_shelx_res_checksum              93406
_shelx_hkl_checksum              35486
_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 1.062
_oxdiff_exptl_absorpt_empirical_full_min 0.950