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_1565062
_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         'C68 H89 Al2 Mn N4 O4, C6 H14'
_chemical_formula_sum            'C74 H103 Al2 Mn N4 O4'
_chemical_formula_weight         1221.50
_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             2019-02-15
_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                 92.256(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8408(5)
_cell_length_b                   27.5925(9)
_cell_length_c                   19.8503(6)
_cell_measurement_reflns_used    5815
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      26.3320
_cell_measurement_theta_min      2.5040
_cell_volume                     7027.7(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)'
_computing_structure_solution    'ShelXT (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 0.988
_diffrn_measured_fraction_theta_max 0.801
_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     -6.00  75.00   1.00   75.17    --   14.27  77.00 -60.00   81
  2  \w      0.00  80.00   1.00   75.17    --   14.27  57.00-150.00   80
;
_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      0.0366274000
_diffrn_orient_matrix_UB_12      0.0057416000
_diffrn_orient_matrix_UB_13      0.0264998000
_diffrn_orient_matrix_UB_21      0.0382631000
_diffrn_orient_matrix_UB_22      0.0046912000
_diffrn_orient_matrix_UB_23      -0.0239865000
_diffrn_orient_matrix_UB_31      -0.0158436000
_diffrn_orient_matrix_UB_32      0.0245968000
_diffrn_orient_matrix_UB_33      -0.0016002000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.801
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            24295
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.801
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.352
_diffrn_reflns_theta_min         2.425
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.262
_exptl_absorpt_correction_T_max  0.959
_exptl_absorpt_correction_T_min  0.918
_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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       block
_exptl_crystal_F_000             2632
_exptl_crystal_size_max          0.434
_exptl_crystal_size_mid          0.284
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.174
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     820
_refine_ls_number_reflns         14077
_refine_ls_number_restraints     94
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.0843
_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^)+(0.1355P)^2^+6.8576P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2249
_refine_ls_wR_factor_ref         0.2668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8735
_reflns_number_total             14077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           2-Mn
_cod_database_code               1565062
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C74 H101 Al2 Mn N4 O4'
_chemical_oxdiff_usercomment     RK237
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.03
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_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
 C174-C173 \\sim C173-C172 \\sim C172-C171 \\sim C171-C170 \\sim C170-C169
 with sigma of 0.02
 C174-C172 \\sim C173-C171 \\sim C172-C170 \\sim C171-C169
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4 \\sim C4: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
C8 \\sim C9 \\sim C5 \\sim C6 \\sim C106 \\sim C107 \\sim C109 \\sim C105 \\sim
C7 \\sim C108: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
C10 \\sim C110: within 2.2A with sigma of 0.01 and sigma for terminal atoms of
0.01
C72 \\sim C71 \\sim C70 \\sim C73 \\sim C74 \\sim C69 \\sim C174 \\sim C173
\\sim C172 \\sim C171 \\sim C170 \\sim C169: within 1A with sigma of 0.01 and
sigma for terminal atoms of 0.01
4. Others
 Sof(C110)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C106)=Sof(H106)=Sof(C107)=
 Sof(H107)=Sof(C108)=Sof(H108)=Sof(C109)=Sof(C105)=Sof(H105)=1-FVAR(1)
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C174)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C173)=Sof(H17D)=Sof(H17E)=
 Sof(C172)=Sof(H17F)=Sof(H17G)=Sof(C171)=Sof(H17H)=Sof(H17I)=Sof(C170)=
 Sof(H17J)=Sof(H17K)=Sof(C169)=Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(2)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C63(H63), C51(H51), C37(H37), C34(H34), C22(H22), C25(H25), C54(H54),
 C66(H66), C8(H8)
5.b Secondary CH2 refined with riding coordinates:
 C72(H72A,H72B), C71(H71A,H71B), C70(H70A,H70B), C73(H73A,H73B), C173(H17D,
 H17E), C172(H17F,H17G), C171(H17H,H17I), C170(H17J,H17K)
5.c Me refined with riding coordinates:
 C74(H74A,H74B,H74C), C69(H69A,H69B,H69C), C174(H17A,H17B,H17C), C169(H16A,
 H16B,H16C)
5.d Aromatic/amide H refined with riding coordinates:
 C13(H13), C42(H42), C59(H59), C61(H61), C60(H60), C47(H47), C20(H20),
 C32(H32), C48(H48), C18(H18), C19(H19), C49(H49), C31(H31), C30(H30), C7(H7),
 C5(H5), C6(H6), C106(H106), C107(H107), C108(H108), C105(H105)
5.e Fitted pentagon refined as free rotating group:
 C7(C8,C9,C5,C6), C106(C107,C108,C109,C105)
5.f Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C39(H39A,H39B,H39C), C23(H23A,H23B,H23C), C15(H15A,H15B,
 H15C), C44(H44A,H44B,H44C), C52(H52A,H52B,H52C), C26(H26A,H26B,H26C), C65(H65A,
 H65B,H65C), C38(H38A,H38B,H38C), C11(H11A,H11B,H11C), C53(H53A,H53B,H53C),
 C27(H27A,H27B,H27C), C40(H40A,H40B,H40C), C24(H24A,H24B,H24C), C36(H36A,H36B,
 H36C), C35(H35A,H35B,H35C), C68(H68A,H68B,H68C), C67(H67A,H67B,H67C), C56(H56A,
 H56B,H56C), C55(H55A,H55B,H55C), C10(H10A,H10B,H10C), C110(H11D,H11E,H11F)
;
_shelx_res_checksum              9516
_shelx_hkl_checksum              31527
_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 1.103
_oxdiff_exptl_absorpt_empirical_full_min 0.899