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_1565067
_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 Cr N4 O8, 3.5(C6 H6)'
_chemical_formula_sum            'C87 H100 Al2 Cr N4 O8'
_chemical_formula_weight         1435.66
_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
_audit_creation_date             2021-04-30
_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                 102.408(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.4194(8)
_cell_length_b                   12.1333(4)
_cell_length_c                   24.9290(9)
_cell_measurement_reflns_used    4344
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      25.5370
_cell_measurement_theta_min      2.5710
_cell_volume                     8099.9(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)'
_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 0.805
_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     -3.00  80.00   1.00   90.96    --   14.27  37.00 120.00   83
  2  \w     -1.00  81.00   1.00   90.96    --   14.27  57.00-180.00   82
;
_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      -0.0038426000
_diffrn_orient_matrix_UB_12      -0.0116218000
_diffrn_orient_matrix_UB_13      0.0266617000
_diffrn_orient_matrix_UB_21      -0.0255227000
_diffrn_orient_matrix_UB_22      -0.0112830000
_diffrn_orient_matrix_UB_23      -0.0112771000
_diffrn_orient_matrix_UB_31      0.0059238000
_diffrn_orient_matrix_UB_32      -0.0561973000
_diffrn_orient_matrix_UB_33      -0.0032456000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_av_unetI/netI     0.1098
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.805
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            28387
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.805
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.299
_diffrn_reflns_theta_min         2.282
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  0.992
_exptl_absorpt_correction_T_min  0.925
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       plate
_exptl_crystal_F_000             3056
_exptl_crystal_size_max          0.484
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.349
_refine_diff_density_min         -0.480
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     951
_refine_ls_number_reflns         16211
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1209
_refine_ls_R_factor_gt           0.0584
_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^)+(0.0510P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1390
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9491
_reflns_number_total             16211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           3-Cr
_cod_database_code               1565067
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C66 H82 N4 O8 Al2 Cr'
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.901
_reflns_odcompleteness_completeness 98.85
_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. Uiso/Uaniso restraints and constraints
C22 \\sim C122 \\sim C21 \\sim C121: within 1A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C75 \\sim C73 \\sim C78 \\sim C77 \\sim C76 \\sim C176 \\sim C175 \\sim C174
\\sim C178 \\sim C177 \\sim C74 \\sim C173: within 1A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C82 \\sim C81 \\sim C80 \\sim C79 \\sim C84 \\sim C83 \\sim C184 \\sim C183
\\sim C182 \\sim C181 \\sim C180 \\sim C179: within 1A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C71 \\sim C70 \\sim C69 \\sim C68 \\sim C67 \\sim C66 \\sim C167 \\sim C166
\\sim C171 \\sim C170 \\sim C169 \\sim C168: within 1A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C185 \\sim C186 \\sim C187 \\sim C188 \\sim C189 \\sim C190 \\sim C85 \\sim C86
\\sim C87 \\sim C88 \\sim C89 \\sim C90: within 2.5A with sigma of 0.01 and
sigma for terminal atoms of 0.01
3. Others
 Sof(H20A)=Sof(C122)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C121)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(H20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=FVAR(1)
 Sof(C176)=Sof(H176)=Sof(C175)=Sof(H175)=Sof(C174)=Sof(H174)=Sof(C173)=
 Sof(H173)=Sof(C178)=Sof(H178)=Sof(C177)=Sof(H177)=1-FVAR(2)
 Sof(C75)=Sof(H75)=Sof(C74)=Sof(H74)=Sof(C73)=Sof(H73)=Sof(C78)=Sof(H78)=
 Sof(C77)=Sof(H77)=Sof(C76)=Sof(H76)=FVAR(2)
 Sof(C167)=Sof(H167)=Sof(C166)=Sof(H166)=Sof(C171)=Sof(H171)=Sof(C170)=
 Sof(H170)=Sof(C169)=Sof(H169)=Sof(C168)=Sof(H168)=1-FVAR(3)
 Sof(C71)=Sof(H71)=Sof(C70)=Sof(H70)=Sof(C69)=Sof(H69)=Sof(C68)=Sof(H68)=
 Sof(C67)=Sof(H67)=Sof(C66)=Sof(H66)=FVAR(3)
 Sof(C184)=Sof(H184)=Sof(C183)=Sof(H183)=Sof(C182)=Sof(H182)=Sof(C181)=
 Sof(H181)=Sof(C180)=Sof(H180)=Sof(C179)=Sof(H179)=1-FVAR(4)
 Sof(C82)=Sof(H82)=Sof(C81)=Sof(H81)=Sof(C80)=Sof(H80)=Sof(C79)=Sof(H79)=
 Sof(C84)=Sof(H84)=Sof(C83)=Sof(H83)=FVAR(4)
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=
 Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90)=0.5*(1-FVAR(6))
 Sof(C185)=Sof(H185)=Sof(C186)=Sof(H186)=Sof(C187)=Sof(H187)=Sof(C188)=
 Sof(H188)=Sof(C189)=Sof(H189)=Sof(C190)=Sof(H190)=0.5*FVAR(6)
4.a Ternary CH refined with riding coordinates:
 C23(H23), C64(H64), C49(H49), C32(H32), C61(H61), C35(H35), C52(H52),
 C20(H20), C20(H20A)
4.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C28(H28), C59(H59), C45(H45), C29(H29), C40(H40), C16(H16),
 C47(H47), C17(H17), C58(H58), C11(H11), C57(H57), C30(H30), C46(H46), C71(H71),
  C70(H70), C69(H69), C68(H68), C67(H67), C66(H66), C185(H185), C186(H186),
 C187(H187), C188(H188), C189(H189), C190(H190), C75(H75), C74(H74), C73(H73),
 C78(H78), C77(H77), C76(H76), C82(H82), C81(H81), C80(H80), C79(H79), C84(H84),
  C83(H83), C176(H176), C175(H175), C174(H174), C173(H173), C178(H178),
 C177(H177), C167(H167), C166(H166), C171(H171), C170(H170), C169(H169),
 C168(H168), C184(H184), C183(H183), C182(H182), C181(H181), C180(H180),
 C179(H179), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90)
4.c Fitted hexagon refined as free rotating group:
 C71(C70,C69,C68,C67,C66), C185(C186,C187,C188,C189,C190), C75(C74,C73,C78,C77,
 C76), C82(C81,C80,C79,C84,C83), C176(C175,C174,C173,C178,C177), C167(C166,C171,
 C170,C169,C168), C184(C183,C182,C181,C180,C179), C85(C86,C87,C88,C89,C90)
4.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C34(H34A,H34B,H34C), C50(H50A,H50B,H50C), C9(H9A,H9B,
 H9C), C38(H38A,H38B,H38C), C33(H33A,H33B,H33C), C25(H25A,H25B,H25C), C7BA(H7BA,
 H7BB,H7BC), C42(H42A,H42B,H42C), C51(H51A,H51B,H51C), C65(H65A,H65B,H65C),
 C53(H53A,H53B,H53C), C62(H62A,H62B,H62C), C13(H13A,H13B,H13C), C63(H63A,H63B,
 H63C), C37(H37A,H37B,H37C), C54(H54A,H54B,H54C), C36(H36A,H36B,H36C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C122(H12A,H12B,H12C), C121(H12D,H12E,H12F)
;
_shelx_res_checksum              68849
_shelx_hkl_checksum              66811
_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 0.945