Tuning Catalytic Activity in the Hydrogenation of Unactivated Olefins with Transition-Metal Oxos as the Lewis Base Component of Frustrated Lewis Pairs
Lambic, Nikola S.; Sommer, Roger D.; Ison, Elon A.; ACS Catalysis 7 (2017) 1170–; doi:10.1021/acscatal.6b03313

data_4514010
_publ_section_title
;
 Tuning Catalytic Activity in the Hydrogenation of Unactivated Olefins
 with Transition-Metal Oxos as the Lewis Base Component of Frustrated
 Lewis Pairs
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              1170
_journal_paper_doi               10.1021/acscatal.6b03313
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C49 H34 Al F15 N3 O Re, C5 H12'
_chemical_formula_sum            'C54 H46 Al F15 N3 O Re'
_chemical_formula_weight         1251.12
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-10-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                67.591(10)
_cell_angle_beta                 72.379(9)
_cell_angle_gamma                69.555(9)
_cell_formula_units_Z            2
_cell_length_a                   12.546(3)
_cell_length_b                   14.078(3)
_cell_length_c                   17.037(5)
_cell_measurement_reflns_used    9676
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.62
_cell_measurement_theta_min      2.41
_cell_volume                     2556.2(11)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0436
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            73730
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.318
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.491
_exptl_absorpt_correction_T_max  0.8776
_exptl_absorpt_correction_T_min  0.5559
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0622 before and 0.0489 after correction.
The Ratio of minimum to maximum transmission is 0.666.
The \l/2 correction factor is 0.00150.

wR2(int) =  0.0579 (selected reflections only, before parameter refinement)

 Cycle  wR2(incid)  wR2(diffr)  Mean wt.
    1     0.0550      0.0529     0.9301
    2     0.0524      0.0522     0.9305
    3     0.0521      0.0521     0.9305
    4     0.0520      0.0520     0.9305
    5     0.0520      0.0520     0.9305
    6     0.0519      0.0520     0.9306
----------------------------------------------
   50     0.0519      0.0519     0.9308

 wR2(int) =  0.0519 (selected reflections only, after parameter refinement)

;
_exptl_crystal_colour            brown
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.625
_exptl_crystal_description       block
_exptl_crystal_F_000             1244
_exptl_crystal_preparation
'Reaction of aluminum Lewis acid with rhenium oxo complex in toluene'
_exptl_crystal_recrystallization_method
'Vapor diffusion of pentane into concentrated toluene solution of complex'
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.097
_exptl_transmission_factor_max   0.84790
_exptl_transmission_factor_min   0.56532
_refine_diff_density_max         6.348
_refine_diff_density_min         -1.295
_refine_diff_density_rms         0.169
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         9018
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0645P)^2^+24.8716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1268
_refine_ls_wR_factor_ref         0.1301
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8345
_reflns_number_total             9018
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03313_si_003.cif
_cod_data_source_block           best
_cod_original_cell_volume        2556.3(11)
_cod_database_code               4514010
_shelx_estimated_absorpt_t_max   0.794
_shelx_estimated_absorpt_t_min   0.498
_exptl_absorpt_special_details
;
Rint 0.0622 for mu = 0 and 0.0489 for mu = 2.490 mm-1
;
_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
C1 \\sim C1A \\sim C2 \\sim C2A \\sim C3 \\sim C3A \\sim C4 \\sim C4A \\sim C5
\\sim C5A \\sim C6 \\sim C6A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
3. Rigid body (RIGU) restrains
 C1, C1A, C2, C2A, C3, C3A, C4, C4A, C5, C5A, C6, C6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C1A(0.5) C2A(0.5) H2A(0.5) C3A(0.5) H3A(0.5) C4A(0.5) H4A(0.5)
 C5A(0.5) H5A(0.5) C6A(0.5) H6A(0.5) C2(0.5) H2(0.5) C3(0.5) H3(0.5) C4(0.5)
 H4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5) C1(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C13(H13A,H13B), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB)
5.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C2(H2), C3(H3), C4(H4),
 C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C16(H16), C18(H18), C25(H25),
 C27(H27)
5.c Fitted hexagon refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A), C2(C3,C4,C5,C6,C1)
5.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C1S(H1SA,H1SB,H1SC), C5S(H5SA,
 H5SB,H5SC)
;
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Adduct
_olex2_submission_special_instructions 'No special instructions were received'