Imine Nitrogen Bridged Binuclear Nickel Complexes via N‒H Bond Activation: Synthesis, Characterization, Unexpected C,N-Coupling Reaction, and Their Catalytic Application in Hydrosilylation of Aldehydes
Wang, Lin; Sun, Hongjian; Li, Xiaoyan; Organometallics 34 (2015) 5175–; doi:10.1021/acs.organomet.5b00734

data_4087929
_publ_section_title
;
 Imine Nitrogen Bridged Binuclear Nickel Complexes via N--H Bond
 Activation: Synthesis, Characterization, Unexpected C,N-Coupling
 Reaction, and Their Catalytic Application in Hydrosilylation of Aldehydes
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              5175
_journal_paper_doi               10.1021/acs.organomet.5b00734
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C30 H36 F4 N2 Ni2 P2 S2'
_chemical_formula_sum            'C30 H36 F4 N2 Ni2 P2 S2'
_chemical_formula_weight         744.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-19
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.157(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0939(4)
_cell_length_b                   31.9239(10)
_cell_length_c                   10.9073(4)
_cell_measurement_temperature    150.15
_cell_volume                     3358.3(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.15
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            STOE
_diffrn_measured_fraction_theta_full 0.934
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS2'
_diffrn_measurement_method       'rotation method'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0200
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 0.934
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            18787
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.627
_diffrn_reflns_theta_min         2.056
_diffrn_source                   'Bruker rotating anode'
_diffrn_source_current           150
_diffrn_source_power             7.500
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.386
_exptl_absorpt_correction_T_max  0.7215
_exptl_absorpt_correction_T_min  0.5072
_exptl_absorpt_correction_type   integration
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.73
_exptl_crystal_size_mid          0.483
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.343
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0025(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     384
_refine_ls_number_reflns         6188
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0296
_refine_ls_R_factor_gt           0.0285
_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^)+(0.0357P)^2^+2.0631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0710
_refine_ls_wR_factor_ref         0.0715
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5906
_reflns_number_total             6188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00734_si_002.cif
_cod_data_source_block           complex8
_cod_database_code               4087929
_shelxl_version_number           2014/6
_shlex_exptl_absorpt_correction_t_min 0.7502
_shlex_exptl_absorpt_correction_t_max 0.7787
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: S1A(0.65) C5A(0.65) H5A(0.65) C6A(0.65) H6A(0.65) C7A(0.65)
 H7A(0.65) S1B(0.35) C5B(0.35) H5B(0.35) C7B(0.35) H7B(0.35) C6B(0.35) H6B(0.35)
3.a Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C6A(H6A), C7A(H7A), C5B(H5B), C7B(H7B), C6B(H6B), C10(H10),
 C11(H11), C12(H12), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23)
3.b Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c), C25(H25a,H25b,H25c), C26(H26a,H26b,H26c),
 C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C29(H29a,H29b,H29c), C30(H30a,H30b,
 H30c)
;