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_1565071
_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
'C67 H87 Al2 Co N4 O4, 1.5(C7 H8), 0.5(C5 H12)'
_chemical_formula_sum            'C80 H105 Al2 Co N4 O4'
_chemical_formula_weight         1299.56
_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             2018-11-16
_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                 96.9581(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0460(2)
_cell_length_b                   25.0267(5)
_cell_length_c                   22.6264(5)
_cell_measurement_reflns_used    7358
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      26.3870
_cell_measurement_theta_min      2.5140
_cell_volume                     7333.1(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 (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 0.986
_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    -16.00  81.00   1.00   36.88    --   14.27   0.00-150.00   97
  2  \w      4.00  67.00   1.00   36.88    --   14.27  19.00 -90.00   63
;
_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      -0.0348329000
_diffrn_orient_matrix_UB_12      -0.0087803000
_diffrn_orient_matrix_UB_13      0.0197142000
_diffrn_orient_matrix_UB_21      0.0225698000
_diffrn_orient_matrix_UB_22      0.0180964000
_diffrn_orient_matrix_UB_23      0.0219558000
_diffrn_orient_matrix_UB_31      -0.0357437000
_diffrn_orient_matrix_UB_32      0.0199800000
_diffrn_orient_matrix_UB_33      -0.0112240000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.801
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25416
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.801
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.349
_diffrn_reflns_theta_min         2.395
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.309
_exptl_absorpt_correction_T_max  0.862
_exptl_absorpt_correction_T_min  0.790
_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    1.177
_exptl_crystal_description       block
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.342
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.206
_refine_diff_density_max         0.638
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         14683
_refine_ls_number_restraints     610
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0600P)^2^+3.8408P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1225
_refine_ls_wR_factor_ref         0.1386
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10344
_reflns_number_total             14683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           3-Co
_cod_original_cell_volume        7333.1(3)
_cod_database_code               1565071
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C36 H34 N2 O7 Al Co2'
_chemical_oxdiff_usercomment     RK169
_reflns_odcompleteness_completeness 98.77
_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
 C181-C175
 1.5 with sigma of 0.02
 C186-C185 \\sim C184-C183
 with sigma of 0.02
 C185-C184 \\sim C183-C182
 with sigma of 0.02
 C176-C181 \\sim C181-C180
 with sigma of 0.02
 C80-C81 \\sim C81-C76
 with sigma of 0.02
3. Restrained planarity
 C181, C178, C179, C177, C180, C176, C175
 with sigma of 0.1
 C78, C81, C80, C75, C79, C76, C77
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
5. Others
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=
 Sof(C80)=Sof(H80)=Sof(C75)=Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77)=0.5*(1-FVAR(2))
 Sof(C178)=Sof(H172)=Sof(C177)=Sof(H171)=Sof(C176)=Sof(H170)=Sof(C175)=
 Sof(C180)=Sof(H174)=Sof(C179)=Sof(H173)=Sof(C181)=Sof(H3AA)=Sof(H3AB)=
 Sof(H3AC)=0.5*FVAR(2)
 Sof(C186)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C185)=Sof(H18D)=Sof(H18E)=
 Sof(C184)=Sof(H18F)=Sof(H18G)=Sof(C183)=Sof(H18H)=Sof(H18I)=Sof(C182)=
 Sof(H18J)=Sof(H18K)=Sof(H18L)=0.5*(1-FVAR(3))
 Sof(C82)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C84)=Sof(H78A)=Sof(H78B)=Sof(C83)=
 Sof(H79A)=Sof(H79B)=Sof(C85)=Sof(H77A)=Sof(H77B)=Sof(C86)=Sof(H76A)=Sof(H76B)=
 Sof(H76C)=0.5*FVAR(3)
 Sof(C165)=Sof(H165)=Sof(C166)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C167)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(3)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C65)=Sof(H65)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(H67C)=FVAR(3)
 Sof(H21A)=Sof(C122)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C123)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=1-FVAR(4)
 Sof(H21)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C53(H53), C36(H36), C21(H21), C21(H21A), C62(H62), C33(H33), C24(H24),
 C65(H65), C50(H50), C165(H165)
6.b Secondary CH2 refined with riding coordinates:
 C84(H78A,H78B), C83(H79A,H79B), C85(H77A,H77B), C185(H18D,H18E), C184(H18F,
 H18G), C183(H18H,H18I)
6.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C60(H60), C30(H30), C12(H12), C29(H29), C48(H48), C46(H46),
 C47(H47), C59(H59), C73(H73), C18(H18), C31(H31), C17(H17), C8(H8), C7(H7),
 C19(H19), C58(H58), C69(H69), C70(H70), C6(H6), C72(H72), C5(H5), C71(H71),
 C9(H9), C178(H172), C177(H171), C176(H170), C180(H174), C179(H173), C78(H78),
 C79(H79), C80(H80), C76(H76), C77(H77)
6.d Fitted hexagon refined as free rotating group:
 C178(C177,C176,C175,C180,C179), C78(C79,C80,C75,C76,C77)
6.e Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C), C10(H10A,H10B,H10C), C37(H37A,H37B,H37C), C54(H54A,H54B,
 H54C), C63(H63A,H63B,H63C), C39(H39A,H39B,H39C), C43(H43A,H43B,H43C), C64(H64A,
 H64B,H64C), C66(H66A,H66B,H66C), C25(H25A,H25B,H25C), C35(H35A,H35B,H35C),
 C38(H38A,H38B,H38C), C26(H26A,H26B,H26C), C14(H14A,H14B,H14C), C34(H34A,H34B,
 H34C), C23(H23A,H23B,H23C), C52(H52A,H52B,H52C), C51(H51A,H51B,H51C), C74(H74A,
 H74B,H74C), C22(H22A,H22B,H22C), C67(H67A,H67B,H67C), C82(H80A,H80B,H80C),
 C181(H3AA,H3AB,H3AC), C81(H81A,H81B,H81C), C86(H76A,H76B,H76C), C186(H18A,H18B,
 H18C), C182(H18J,H18K,H18L), C166(H16A,H16B,H16C), C167(H16D,H16E,H16F),
 C122(H12A,H12B,H12C), C123(H12D,H12E,H12F)
;
_shelx_res_checksum              49449
_shelx_hkl_checksum              37833
_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 1.052
_oxdiff_exptl_absorpt_empirical_full_min 0.959