Organomagnesium amide catalyzed cross-dehydrocoupling of organosilanes with amines.
Baishya, Ashim; Peddarao, Thota; Nembenna, Sharanappa; Dalton transactions (Cambridge, England : 2003)  (2017) –; doi:10.1039/c7dt00806f

data_7043787
_publ_section_title
;
 Organomagnesium amide catalyzed cross-dehydrocoupling of organosilanes
 with amines.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/c7dt00806f
_journal_year                    2017
_chemical_formula_moiety         'C35 H51 Mg N3 Si2, C7 H8'
_chemical_formula_sum            'C42 H59 Mg N3 Si2'
_chemical_formula_weight         686.41
_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
_audit_creation_date             2017-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-03-24 deposited with the CCDC.
2017-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                72.347(3)
_cell_angle_beta                 76.154(3)
_cell_angle_gamma                89.454(3)
_cell_formula_units_Z            2
_cell_length_a                   9.4770(4)
_cell_length_b                   12.9087(6)
_cell_length_c                   18.2858(8)
_cell_measurement_reflns_used    8712
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.05
_cell_measurement_theta_min      3.69
_cell_volume                     2064.92(16)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0567
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            31544
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.113
_diffrn_reflns_theta_min         3.685
_exptl_absorpt_coefficient_mu    0.132
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5830
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0840 before and 0.0484 after correction.
The Ratio of minimum to maximum transmission is 0.7815.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.104
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.505
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     576
_refine_ls_number_reflns         11856
_refine_ls_number_restraints     369
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0836
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0620P)^2^+0.8207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1242
_refine_ls_wR_factor_ref         0.1436
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8156
_reflns_number_total             11856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt00806f2.cif
_cod_data_source_block           retry
_cod_database_code               7043787
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 C1A-C1B
 1.51 with sigma of 0.02
 C1H-C1I
 1.51 with sigma of 0.02
 C1O-C1P
 1.51 with sigma of 0.02
 C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G \\sim C1G-C1B
 with sigma of 0.02
 C1B-C1F \\sim C1B-C1D \\sim C1G-C1E \\sim C1C-C1G \\sim C1D-C1F \\sim C1C-C1E
 with sigma of 0.04
 C1A-C1G \\sim C1A-C1C
 with sigma of 0.04
 C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1N \\sim C1N-C1I
 with sigma of 0.02
 C1I-C1M \\sim C1I-C1K \\sim C1N-C1L \\sim C1J-C1N \\sim C1K-C1M \\sim C1J-C1L
 with sigma of 0.04
 C1H-C1N \\sim C1H-C1J
 with sigma of 0.04
 C1P-C1Q \\sim C1Q-C1R \\sim C1R-C1S \\sim C1S-C1T \\sim C1T-C1U \\sim C1U-C1P
 with sigma of 0.02
 C1P-C1T \\sim C1P-C1R \\sim C1U-C1S \\sim C1Q-C1U \\sim C1R-C1T \\sim C1Q-C1S
 with sigma of 0.04
 C1O-C1U \\sim C1O-C1Q
 with sigma of 0.04
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma of 0.1
 C1H, C1I, C1J, C1K, C1L, C1M, C1N
 with sigma of 0.1
 C1O, C1P, C1Q, C1R, C1S, C1T, C1U
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C1H \\sim C1I \\sim C1J \\sim C1K \\sim C1L \\sim C1M \\sim C1N: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C1O \\sim C1P \\sim C1Q \\sim C1R \\sim C1S \\sim C1T \\sim C1U: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1H, C1I, C1J, C1K, C1L, C1M, C1N
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1O, C1P, C1Q, C1R, C1S, C1T, C1U
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1G, C1A, C1B, C1C, C1D, C1F, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1N, C1H, C1I, C1J, C1K, C1M, C1L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1C, C1G, C1D, C1F, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C1A(0.4) H1AD(0.4) H1AE(0.4) H1AF(0.4) C1B(0.4) C1C(0.4) H1C(0.4)
 C1D(0.4) H1D(0.4) C1E(0.4) H1E(0.4) C1F(0.4) H1F(0.4) C1G(0.4) H1G(0.4)
 C1H(0.4) H1HA(0.4) H1HB(0.4) H1HC(0.4) C1I(0.4) C1J(0.4) H1J(0.4) C1K(0.4)
 H1K(0.4) C1L(0.4) H1L(0.4) C1M(0.4) H1M(0.4) C1N(0.4) H1N(0.4) C1O(0.2)
 H1OA(0.2) H1OB(0.2) H1OC(0.2) C1P(0.2) C1Q(0.2) H1Q(0.2) C1R(0.2) H1R(0.2)
 C1S(0.2) H1S(0.2) C1T(0.2) H1T(0.2) C1U(0.2) H1U(0.2)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C24(H24), C23(H23), C6(H6), C25(H25), C18(H18), C16(H16),
 C10(H10), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G), C1J(H1J), C1K(H1K),
  C1L(H1L), C1M(H1M), C1N(H1N), C1Q(H1Q), C1R(H1R), C1S(H1S), C1T(H1T), C1U(H1U)
7.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C29(H29A,H29B,H29C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31C), C33(H33A,
 H33B,H33C), C15(H15A,H15B,H15C), C2AA(H2AA,H2AB,H2AC), C20(H20A,H20B,H20C),
 C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C1AA(H1AA,H1AB,H1AC), C1A(H1AD,H1AE,
 H1AF), C1H(H1HA,H1HB,H1HC), C1O(H1OA,H1OB,H1OC)
;
_shelx_res_checksum              64258
_olex2_submission_special_instructions 'No special instructions were received'