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_1565072
_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         'C73 H97 Al2 N4 O5 Re, 1.5(C5 H12)'
_chemical_formula_sum            'C80.5 H115 Al2 N4 O5 Re'
_chemical_formula_weight         1458.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   45.706(2)
_cell_length_b                   17.2177(17)
_cell_length_c                   20.3938(17)
_cell_measurement_reflns_used    8523
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      28.1250
_cell_measurement_theta_min      2.9350
_cell_volume                     16049(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)'
_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 0.990
_diffrn_measured_fraction_theta_max 0.802
_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    -41.00  68.50   0.75   31.82    --   14.43   0.00 -60.00  146
;
_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      -0.0247569000
_diffrn_orient_matrix_UB_12      0.0044602000
_diffrn_orient_matrix_UB_13      0.0260125000
_diffrn_orient_matrix_UB_21      0.0074329000
_diffrn_orient_matrix_UB_22      0.0148984000
_diffrn_orient_matrix_UB_23      -0.0077862000
_diffrn_orient_matrix_UB_31      -0.0318458000
_diffrn_orient_matrix_UB_32      0.0000098000
_diffrn_orient_matrix_UB_33      -0.0219558000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0589
_diffrn_reflns_av_unetI/netI     0.0865
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.802
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            36505
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.802
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.375
_diffrn_reflns_theta_min         2.361
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.585
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.520
_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    1.208
_exptl_crystal_description       plate
_exptl_crystal_F_000             6136
_exptl_crystal_size_max          0.561
_exptl_crystal_size_mid          0.356
_exptl_crystal_size_min          0.069
_refine_diff_density_max         1.523
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.150
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     956
_refine_ls_number_reflns         16110
_refine_ls_number_restraints     194
_refine_ls_restrained_S_all      1.147
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0766
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0394P)^2^+76.8007P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1503
_refine_ls_wR_factor_ref         0.1662
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11818
_reflns_number_total             16110
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04940b3.cif
_cod_data_source_block           3-Re
_cod_original_formula_sum        'C80.50 H115 Al2 N4 O5 Re'
_cod_database_code               1565072
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C73 H63 N4 O5 Al2 Re'
_chemical_oxdiff_usercomment     RK238
_reflns_odcompleteness_completeness 99.14
_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
 C79-C80 = C80-C81 = C81-C82 = C82-C83
 1.5 with sigma of 0.01
 C179-C180 = C180-C181 = C181-C182 = C182-C183
 1.5 with sigma of 0.01
 C79-C81 = C80-C82 = C81-C83
 2.46 with sigma of 0.02
 C179-C181 = C180-C182 = C181-C183
 2.46 with sigma of 0.02
 C74-C75 = C75-C76 = C76-C77 = C77-C78
 1.5 with sigma of 0.01
 C174-C175 = C175-C176 = C176-C177 = C177-C178
 1.5 with sigma of 0.01
 C74-C76 = C76-C78
 2.46 with sigma of 0.02
 C174-C176 = C176-C178
 2.46 with sigma of 0.02
 C274-C275 = C275-C276 = C276-C277 = C277-C278
 1.5 with sigma of 0.01
 C274-C276 = C276-C278
 2.46 with sigma of 0.02
 C79-C80 \\sim C80-C81 \\sim C81-C82 \\sim C82-C83
 with sigma of 0.02
 C79-C81 \\sim C80-C82 \\sim C81-C83
 with sigma of 0.02
 C179-C180 \\sim C180-C181 \\sim C181-C182 \\sim C182-C183
 with sigma of 0.02
 C179-C181 \\sim C180-C182 \\sim C181-C183
 with sigma of 0.02
 C74-C76 \\sim C75-C77 \\sim C76-C78
 with sigma of 0.02
 C174-C176 \\sim C175-C177 \\sim C176-C178
 with sigma of 0.02
 C74-C75 \\sim C75-C76 \\sim C76-C77 \\sim C77-C78
 with sigma of 0.02
 C174-C175 \\sim C175-C176 \\sim C176-C177 \\sim C177-C178
 with sigma of 0.02
 C274-C276 \\sim C275-C277 \\sim C276-C278
 with sigma of 0.02
 C274-C275 \\sim C275-C276 \\sim C276-C277 \\sim C277-C278
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C43 \\sim C143 \\sim C144 \\sim C44: within 1A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C31 \\sim C32 \\sim C131 \\sim C132: within 1A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C180 \\sim C181 \\sim C183 \\sim C179 \\sim C182 \\sim C80 \\sim C81 \\sim C79
\\sim C82 \\sim C83: within 1.3A with sigma of 0.01 and sigma for terminal
atoms of 0.01
C59 \\sim C61 \\sim C60 \\sim C159 \\sim C161 \\sim C160: within 1.2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C277 \\sim C278 \\sim C276 \\sim C274 \\sim C275 \\sim C78 \\sim C77 \\sim C76
\\sim C75 \\sim C74 \\sim C178 \\sim C177 \\sim C176 \\sim C175 \\sim C174:
within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Others
 1*[Sof(C277)+Sof(H27A)+Sof(H27B)+Sof(C278)+Sof(H27C)+Sof(H27D)+Sof(H27E)+
 Sof(C276)+Sof(H27F)+Sof(H27G)+Sof(C274)+Sof(H27H)+Sof(H27I)+Sof(H27J)+
 Sof(C275)+Sof(H27K)+Sof(H27L)]+1*[Sof(C78)+Sof(H78A)+Sof(H78B)+Sof(H78C)+
 Sof(C77)+Sof(H77A)+Sof(H77B)+Sof(C76)+Sof(H76A)+Sof(H76B)+Sof(C75)+Sof(H75A)+
 Sof(H75B)+Sof(C74)+Sof(H74A)+Sof(H74B)+Sof(H74C)]+1*[Sof(C178)+Sof(H17D)+
 Sof(H17E)+Sof(H17F)+Sof(C177)+Sof(H17G)+Sof(H17H)+Sof(C176)+Sof(H17I)+
 Sof(H17J)+Sof(C175)+Sof(H17K)+Sof(H17L)+Sof(C174)+Sof(H17M)+Sof(H17N)+
 Sof(H17O)]=1 with esd of 0
 Sof(H42A)=Sof(C144)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C143)=Sof(H14G)=
 Sof(H14H)=Sof(H14I)=1-FVAR(1)
 Sof(H42)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 Sof(H44C)=FVAR(1)
 Sof(H30A)=Sof(C131)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C132)=Sof(H13G)=
 Sof(H13H)=Sof(H13I)=1-FVAR(2)
 Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=FVAR(2)
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C79)=Sof(H79A)=
 Sof(H79B)=Sof(H79C)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=Sof(H83A)=Sof(H83B)=
 Sof(H83C)=0.5*(1-FVAR(4))
 Sof(C180)=Sof(H18A)=Sof(H18B)=Sof(C181)=Sof(H18C)=Sof(H18D)=Sof(C183)=
 Sof(H18E)=Sof(H18F)=Sof(H18G)=Sof(C179)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C182)=Sof(H18H)=Sof(H18I)=0.5*FVAR(4)
 Sof(C277)=Sof(H27A)=Sof(H27B)=Sof(C278)=Sof(H27C)=Sof(H27D)=Sof(H27E)=
 Sof(C276)=Sof(H27F)=Sof(H27G)=Sof(C274)=Sof(H27H)=Sof(H27I)=Sof(H27J)=
 Sof(C275)=Sof(H27K)=Sof(H27L)=FVAR(4)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(C76)=
 Sof(H76A)=Sof(H76B)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C74)=Sof(H74A)=Sof(H74B)=
 Sof(H74C)=FVAR(5)
 Sof(C178)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C177)=Sof(H17G)=Sof(H17H)=
 Sof(C176)=Sof(H17I)=Sof(H17J)=Sof(C175)=Sof(H17K)=Sof(H17L)=Sof(C174)=
 Sof(H17M)=Sof(H17N)=Sof(H17O)=FVAR(6)
 Sof(C159)=Sof(H159)=Sof(C161)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C160)=
 Sof(H16G)=Sof(H16H)=Sof(H16I)=1-FVAR(7)
 Sof(C59)=Sof(H59)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C60)=Sof(H60A)=
 Sof(H60B)=Sof(H60C)=FVAR(7)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C68(H68), C39(H39), C59(H59), C71(H71), C42(H42), C42(H42A),
 C56(H56), C30(H30), C30(H30A), C159(H159)
5.b Secondary CH2 refined with riding coordinates:
 C180(H18A,H18B), C181(H18C,H18D), C182(H18H,H18I), C80(H80A,H80B), C81(H81A,
 H81B), C82(H82A,H82B), C277(H27A,H27B), C276(H27F,H27G), C275(H27K,H27L),
 C77(H77A,H77B), C76(H76A,H76B), C75(H75A,H75B), C177(H17G,H17H), C176(H17I,
 H17J), C175(H17K,H17L)
5.c Me refined with riding coordinates:
 C278(H27C,H27D,H27E), C274(H27H,H27I,H27J), C78(H78A,H78B,H78C), C74(H74A,
 H74B,H74C), C178(H17D,H17E,H17F), C174(H17M,H17N,H17O)
5.d Aromatic/amide H refined with riding coordinates:
 C25(H25), C47(H47), C18(H18), C64(H64), C37(H37), C36(H36), C35(H35),
 C23(H23), C24(H24), C52(H52), C65(H65), C54(H54), C66(H66), C53(H53)
5.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C15(H15A,H15B,H15C), C28(H28A,H28B,H28C), C45(H45A,H45B,H45C), C49(H49A,
 H49B,H49C), C57(H57A,H57B,H57C), C16(H16A,H16B,H16C), C29(H29A,H29B,H29C),
 C40(H40A,H40B,H40C), C14(H14A,H14B,H14C), C70(H70A,H70B,H70C), C73(H73A,H73B,
 H73C), C41(H41A,H41B,H41C), C72(H72A,H72B,H72C), C31(H31A,H31B,H31C), C69(H69A,
 H69B,H69C), C32(H32A,H32B,H32C), C58(H58A,H58B,H58C), C43(H43A,H43B,H43C),
 C44(H44A,H44B,H44C), C144(H14D,H14E,H14F), C143(H14G,H14H,H14I), C131(H13D,
 H13E,H13F), C132(H13G,H13H,H13I), C183(H18E,H18F,H18G), C179(H17A,H17B,H17C),
 C79(H79A,H79B,H79C), C83(H83A,H83B,H83C), C61(H61A,H61B,H61C), C60(H60A,H60B,
 H60C), C161(H16D,H16E,H16F), C160(H16G,H16H,H16I)
;
_shelx_res_checksum              26496
_shelx_hkl_checksum              62388
_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 1.162
_oxdiff_exptl_absorpt_empirical_full_min 0.821