Side Arm Twist on Zn-Catalyzed Hydrosilylative Reduction of CO2 to Formate and Methanol Equivalents with High Selectivity and Activity
Feng, Guoqin; Du, Chongyang; Xiang, Li; del Rosal, Iker; Li, Guangyu; Leng, Xuebing; Chen, Eugene Y.-X.; Maron, Laurent; Chen, Yaofeng; ACS Catalysis 8 (2018) 4710–; doi:10.1021/acscatal.8b01033

data_4515598
_publ_section_title
;
 Side Arm Twist on Zn-Catalyzed Hydrosilylative Reduction of CO2 to
 Formate and Methanol Equivalents with High Selectivity and Activity
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              4710
_journal_paper_doi               10.1021/acscatal.8b01033
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C52 H86 N6 O4 Zn2, C3 H7'
_chemical_formula_sum            'C55 H93 N6 O4 Zn2'
_chemical_formula_weight         1033.18
_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_Int_Tables_number      2
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                76.808(1)
_cell_angle_beta                 73.779(1)
_cell_angle_gamma                84.324(1)
_cell_formula_units_Z            2
_cell_length_a                   12.7688(2)
_cell_length_b                   13.8810(3)
_cell_length_c                   17.4955(3)
_cell_measurement_reflns_used    9753
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      60.60
_cell_measurement_theta_min      4.16
_cell_volume                     2896.90(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.9913
_diffrn_measured_fraction_theta_max 0.9913
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            44316
_diffrn_reflns_theta_full        60.6107
_diffrn_reflns_theta_max         60.61
_diffrn_reflns_theta_min         4.16
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.848
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6015
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1155 before and 0.0602 after correction.
The Ratio of minimum to maximum transmission is 0.8000.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.1844
_exptl_crystal_description       block
_exptl_crystal_F_000             1104.8502
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.6113
_refine_diff_density_min         -0.5336
_refine_diff_density_rms         0.0580
_refine_ls_d_res_high            0.7698
_refine_ls_d_res_low             9.2489
_refine_ls_goodness_of_fit_ref   1.0462
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    140
_refine_ls_number_parameters     633
_refine_ls_number_reflns         13191
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0462
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.0011
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0529P)^2^+1.6474P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -15
_reflns_limit_k_max              18
_reflns_limit_k_min              -17
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                11861
_reflns_number_total             13191
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs8b01033_si_002.cif
_cod_data_source_block           L2ZnO2CH
_cod_database_code               4515598
_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. Others
 Fixed Sof: H52(0.5) H52a(0.5) O4(0.5) O5(0.5)
3.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C20(H20), C23(H23), C33(H33), C36(H36), C45(H45), C48(H48)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6a,H6b), C7(H7a,H7b), C31(H31a,H31b), C32(H32a,H32b), C54(H54a,H54b),
 C55(H55a,H55b)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C16(H16), C17(H17), C18(H18), C28(H28), C41(H41), C42(H42), C43(H43),
 C51(H51), C52(H52), C52(H52a)
3.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C9(H9a,H9b,H9c), C10(H10a,H10b,H10c),
 C12(H12a,H12b,H12c), C13(H13a,H13b,H13c), C21(H21a,H21b,H21c), C22(H22a,H22b,
 H22c), C24(H24a,H24b,H24c), C25(H25a,H25b,H25c), C26(H26a,H26b,H26c), C30(H30a,
 H30b,H30c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c), C37(H37a,H37b,H37c),
 C38(H38a,H38b,H38c), C46(H46a,H46b,H46c), C47(H47a,H47b,H47c), C49(H49a,H49b,
 H49c), C50(H50a,H50b,H50c), C53(H53a,H53b,H53c)
;
_olex2_submission_special_instructions 'No special instructions were received'