Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.
Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter; Dalton transactions (Cambridge, England : 2003) 47 (2018) 2581–2588; doi:10.1039/c7dt04155a

data_7045316
_publ_section_title
;
 Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt
 hydride for Kumada coupling reactions.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2581
_journal_page_last               2588
_journal_paper_doi               10.1039/c7dt04155a
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety         '2(C51 H64 Cl2 Co N4 P3 Si2), C4 H10 O'
_chemical_formula_sum            'C106 H138 Cl4 Co2 N8 O P6 Si4'
_chemical_formula_weight         2098.08
_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
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-31
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.06 svn.r2239, GUI svn.r4109)
;
_audit_update_record
;
2017-08-21 deposited with the CCDC.
2018-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                99.180(3)
_cell_angle_beta                 99.723(3)
_cell_angle_gamma                103.830(3)
_cell_formula_units_Z            2
_cell_length_a                   13.9433(5)
_cell_length_b                   17.2555(7)
_cell_length_c                   24.5173(10)
_cell_measurement_reflns_used    8356
_cell_measurement_temperature    150.15
_cell_measurement_theta_max      61.82
_cell_measurement_theta_min      3.34
_cell_volume                     5521.0(4)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
olex2.refine (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            DECTRIS
_diffrn_measured_fraction_theta_full 0.955
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_device       '4-circle goniometer'
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.1348
_diffrn_reflns_av_unetI/netI     0.1612
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            49093
_diffrn_reflns_theta_full        65.08
_diffrn_reflns_theta_max         65.08
_diffrn_reflns_theta_min         2.70
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    4.862
_exptl_absorpt_correction_T_max  0.8170
_exptl_absorpt_correction_T_min  0.5543
_exptl_absorpt_correction_type   integration
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2212
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.930
_refine_diff_density_min         -1.047
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.847
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1232
_refine_ls_number_reflns         17989
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      0.846
_refine_ls_R_factor_all          0.1749
_refine_ls_R_factor_gt           0.0949
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1944P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2452
_refine_ls_wR_factor_ref         0.3026
_reflns_number_gt                7692
_reflns_number_total             17989
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7dt04155a2.cif
_cod_data_source_block           sun17
_cod_depositor_comments
'Adding full bibliography for 7045316--7045318.cif.'
_cod_database_code               7045316
_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, All C(H,H,H,H,H) groups
2. Restrained distances
 C104-C103 = O1-C103 = O1-C105 = C106-C105
 1.54 with sigma of 0.02
 C104-O1
 2.5 with sigma of 0.02
 C103-C105
 2.5 with sigma of 0.02
 O1-C106
 2.5 with sigma of 0.02
 C04B-C03B = O1B-C03B = O1B-C5B = C6B-C5B
 1.54 with sigma of 0.02
 C6B-O1B
 2.5 with sigma of 0.02
 C5B-C03B
 2.5 with sigma of 0.02
 O1B-C04B
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C73') \\sim Ueq, Uanis(C74') \\sim Ueq, Uanis(C75') \\sim Ueq,
Uanis(C76') \\sim Ueq, Uanis(C77') \\sim Ueq, Uanis(C78') \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uiso(C103) = Uiso(C104) = Uiso(O1) = Uiso(C105) = Uiso(C106)
4. Others
 Sof(C73')=Sof(C74')=Sof(H74')=Sof(C75')=Sof(H75')=Sof(C76')=Sof(H76')=
 Sof(C77')=Sof(H77')=Sof(C78')=Sof(H78')=1-FVAR(1)
 Sof(C73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=Sof(C77)=
 Sof(H77)=Sof(C78)=Sof(H78)=FVAR(1)
 Fixed Sof: O1B(0.5) C03B(0.5) H03A(0.5) H03B(0.5) C04B(0.5) H04A(0.5)
 H04B(0.5) H04C(0.5) C5B(0.5) H5BA(0.5) H5BB(0.5) C6B(0.5) H6BA(0.5) H6BB(0.5)
 H6BC(0.5) O1(0.5) C103(0.5) H10J(0.5) H10K(0.5) C104(0.5) H10L(0.5) H10M(0.5)
 H10N(0.5) C105(0.5) H10O(0.5) H10P(0.5) C106(0.5) H10Q(0.5) H10R(0.5) H10S(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C21(H21A,H21B), C65(H65A,H65B), C72(H72A,H72B), C03B(H03A,
 H03B), C5B(H5BA,H5BB), C103(H10J,H10K), C105(H10O,H10P)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24), C25(H25),
  C26(H26), C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33),
 C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C54(H54), C55(H55), C56(H56),
  C57(H57), C58(H58), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64),
 C67(H67), C68(H68), C69(H69), C70(H70), C80(H80), C81(H81), C82(H82), C83(H83),
  C84(H84), C91(H91), C92(H92), C93(H93), C94(H94), C95(H95), C74(H74),
 C75(H75), C76(H76), C77(H77), C78(H78), C74'(H74'), C75'(H75'), C76'(H76'),
 C77'(H77'), C78'(H78')
5.c Fitted hexagon refined as free rotating group:
 C73(C74,C75,C76,C77,C78), C73'(C74',C75',C76',C77',C78')
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C),
 C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C04B(H04A,H04B,H04C), C6B(H6BA,
 H6BB,H6BC), C104(H10L,H10M,H10N), C106(H10Q,H10R,H10S)
;
_olex2_submission_special_instructions 'No special instructions were received'