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_4515599
_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         'C51 H86 N6 O2 Zn2'
_chemical_formula_sum            'C51 H86 N6 O2 Zn2'
_chemical_formula_weight         945.99
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-12-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                98.9000(10)
_cell_angle_beta                 90.9840(10)
_cell_angle_gamma                119.0520(10)
_cell_formula_units_Z            4
_cell_length_a                   16.1366(3)
_cell_length_b                   16.5978(3)
_cell_length_c                   23.3164(4)
_cell_measurement_reflns_used    9134
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.90
_cell_measurement_theta_min      3.90
_cell_volume                     5362.53(18)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0442
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            73911
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.899
_diffrn_reflns_theta_min         2.899
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.902
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6171
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1235 before and 0.0612 after correction.
The Ratio of minimum to maximum transmission is 0.8219.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.172
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.937
_refine_diff_density_min         -0.840
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1176
_refine_ls_number_reflns         20258
_refine_ls_number_restraints     163
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0712P)^2^+4.8320P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1320
_refine_ls_wR_factor_ref         0.1380
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17868
_reflns_number_total             20258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01033_si_002.cif
_cod_data_source_block           L2Zn(O2CH)(H)ZnL2
_cod_original_cell_volume        5362.52(17)
_cod_database_code               4515599
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.881
_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
 C9-C8
 1.53 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
N12 \\sim C84 \\sim C85 \\sim C86: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C71 \\sim C72 \\sim C73: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
N12 \\sim C87 \\sim C88 \\sim C89 \\sim C87' \\sim C88' \\sim C89': within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C85) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C89) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C88')
\\sim Ueq, Uanis(C87') \\sim Ueq, Uanis(C89') \\sim Ueq: with sigma of 0.005
and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: C87(0.5) H87(0.5) C88(0.5) H88A(0.5) H88B(0.5) H88C(0.5) C89(0.5)
 H89A(0.5) H89B(0.5) H89C(0.5) C87'(0.5) H87'(0.5) C88'(0.5) H88D(0.5)
 H88E(0.5) H88F(0.5) C89'(0.5) H89D(0.5) H89E(0.5) H89F(0.5)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C20(H20), C23(H23), C33(H33), C36(H36), C45(H45), C48(H48),
 C59(H59), C62(H62), C71(H71), C74(H74), C84(H84), C96(H96), C99(H99), C87(H87),
  C87'(H87')
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C31(H31A,H31B), C32(H32A,H32B), C57(H57A,H57B),
 C58(H58A,H58B), C82(H82A,H82B), C83(H83A,H83B)
5.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), C54(H54), C67(H67), C68(H68), C69(H69), C79(H79), C92(H92), C93(H93),
  C94(H94), C102(H102)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10G,H10H,H10I),
 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), C52(H52A,H52B,H52C), C56(H56A,H56B,H56C), C60(H60A,
 H60B,H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C77(H77A,H77B,H77C), C81(H81A,H81B,H81C), C85(H85A,H85B,H85C), C86(H86A,
 H86B,H86C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C100(H10A,H10B,H10C),
 C101(H10D,H10E,H10F), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C88'(H88D,H88E,
 H88F), C89'(H89D,H89E,H89F)
;
_shelx_res_checksum              36508
_shelx_hkl_checksum              66990
_olex2_submission_special_instructions 'No special instructions were received'