Ligand-Metal Cooperativity in Quinonoid Based Nickel(II) and Cobalt(II) Complexes for Catalytic Hydrosilylative Reduction of Nitrile to Amine: Electron Transfer and Mechanistic Insight
Biswas, Bhaskar; Paramanik, Krishnendu; Banerjee, Nilaj; Sarkar, Gayetri; Chatterjee, Souvik; Roy, Suvojit; Panda, Subhra Jyoti; Purohit, Chandra Shekhar; Das, Hari Sankar; Dalton Transactions  (2023) –; doi:10.1039/D3DT00090G

data_7712592
_publ_section_title
;
 Ligand-Metal Cooperativity in Quinonoid Based Nickel(II) and Cobalt(II)
 Complexes for Catalytic Hydrosilylative Reduction of Nitrile to Amine:
 Electron Transfer and Mechanistic Insight
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00090G
_journal_year                    2023
_chemical_formula_moiety         '1(C42 H54 N2 Ni O2 S2)'
_chemical_formula_sum            'C42 H54 N2 Ni O2 S2'
_chemical_formula_weight         741.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-03-02
_audit_creation_method
;
Olex2 1.5-dev
(compiled 2023.02.27 svn.rf166f9f3 for OlexSys, GUI svn.r6444)
;
_audit_update_record
;
2023-03-07 deposited with the CCDC.	2023-03-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.156(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.7335(11)
_cell_length_b                   13.5133(7)
_cell_length_c                   12.4009(7)
_cell_measurement_reflns_used    11482
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      32.1660
_cell_measurement_theta_min      3.5740
_cell_volume                     3946.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -54.00  25.00   0.50   10.00    --    7.48 -70.00-124.00  158
  2  \w    -16.00  55.00   0.50   10.00    --   -8.10  70.00   6.00  142
  3  \w      1.00  27.00   0.50   10.00    --    7.48 -99.00-150.00   52
  4  \w    -30.00   6.00   0.50   10.00    --   -8.10  77.00 -30.00   72
  5  \w    -11.00  15.00   0.50   10.00    --   -8.10 -77.00 120.00   52
  6  \w    -14.00  16.00   0.50   10.00    --   -8.10  19.00 150.00   60
  7  \w     34.00  61.00   0.50   10.00    --   -8.10  19.00 150.00   54
  8  \w    -23.00   3.00   0.50   10.00    --   -8.10 -57.00   0.00   52
  9  \w    -41.00  11.00   0.50   10.00    --   -8.10 -77.00  90.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0601
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            22011
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.000
_diffrn_reflns_theta_min         3.311
_exptl_absorpt_coefficient_mu    0.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.52a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       block
_exptl_crystal_F_000             1584
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow vapour diffusion'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.281
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.476(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     888
_refine_ls_number_reflns         8756
_refine_ls_number_restraints     877
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0447
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0515P)^2^+2.2469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1145
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    0.881
_reflns_Friedel_fraction_max     0.835
_reflns_number_gt                7313
_reflns_number_total             8756
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00090g2.cif
_cod_data_source_block           csp-ska-kp2_auto
_cod_database_code               7712592
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.852
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.524(19)
 0.476(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C6) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C20A)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C26A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C3A) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C34A)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(S2A)=Sof(S1A)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C15A)=Sof(C16A)=
 Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(N1A)=Sof(C2A)=Sof(Ni1A)=Sof(C1A)=Sof(C3A)=Sof(H3A)=Sof(O2A)=
 Sof(O1A)=Sof(N2A)=Sof(C6A)=Sof(C4A)=Sof(C22A)=Sof(C23A)=Sof(C36A)=Sof(C37A)=
 Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=
 Sof(C41A)=Sof(C5A)=Sof(H5A)=Sof(C11A)=Sof(C7A)=Sof(C27A)=Sof(C24A)=Sof(H24A)=
 Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=Sof(C26A)=Sof(H26A)=Sof(C32A)=Sof(C25A)=Sof(C33A)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35A)=
 Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C28A)=Sof(C42A)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(1)
 Sof(S1)=Sof(O2)=Sof(N1)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=
 Sof(H5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=
 Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=
 Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(C26)=Sof(H26)=
 Sof(C27)=Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=
 Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(Ni1)=Sof(S2)=Sof(O1)=Sof(N2)=Sof(C36)=
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=
 Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(1)
6.a Riding coordinates:
 C34(H34A,H34B,H34C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C16(H16), C17(H17), C18(H18), C19(H19), C24(H24), C26(H26),
 C37(H37), C38(H38), C39(H39), C40(H40), C16A(H16A), C17A(H17A), C18A(H18A),
 C19A(H19A), C3A(H3A), C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C5A(H5A),
  C24A(H24A), C26A(H26A)
6.c Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C19,C20), C15A(C16A,C17A,C18A,C19A,C20A)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C35(H35A,
 H35B,H35C), C42(H42A,H42B,H42C), C21A(H21D,H21E,H21F), C12A(H12D,H12E,H12F),
 C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10D,H10E,H10F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F),
 C35A(H35D,H35E,H35F), C42A(H42D,H42E,H42F), C29A(H29D,H29E,H29F), C30A(H30D,
 H30E,H30F), C31A(H31D,H31E,H31F)
;
_shelx_res_checksum              72583
_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
;