Regioselectivity of Addition to the Azavinylidene Ligand in Tp′W(CO)(η2-HC≡CH)(N═CHMe): Electrophilic Addition versus Oxidation and Radical Coupling
Beattie, Ross J.; White, Peter S.; Templeton, Joseph L.; Organometallics 35 (2015) 32–; doi:10.1021/acs.organomet.5b00678

data_4087886
_publ_section_title
;
 Regioselectivity of Addition to the Azavinylidene Ligand in
 Tp&#x2032;W(CO)(\h2-HC\\tb CH)(N&#x2550;CHMe): Electrophilic Addition
 versus Oxidation and Radical Coupling
;
_journal_issue                   1
_journal_name_full               Organometallics
_journal_page_first              32
_journal_paper_doi               10.1021/acs.organomet.5b00678
_journal_volume                  35
_journal_year                    2015
_chemical_formula_moiety         'C21 H31 B N7 O W, C7 H18 N, 2(C F3 O3 S)'
_chemical_formula_sum            'C30 H49 B F6 N8 O7 S2 W'
_chemical_formula_weight         1006.55
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-07-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                83.5274(19)
_cell_angle_beta                 78.803(2)
_cell_angle_gamma                89.4183(19)
_cell_formula_units_Z            2
_cell_length_a                   8.1886(3)
_cell_length_b                   12.4277(4)
_cell_length_c                   20.3819(7)
_cell_measurement_reflns_used    9315
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.49
_cell_measurement_theta_min      2.22
_cell_volume                     2021.58(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24402
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        66.635
_diffrn_reflns_theta_max         66.634
_diffrn_reflns_theta_min         2.224
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.976
_exptl_absorpt_correction_T_max  0.8537
_exptl_absorpt_correction_T_min  0.4373
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0742 before and 0.0488 after correction.
The Ratio of minimum to maximum transmission is 0.5122.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.654
_exptl_crystal_description       block
_exptl_crystal_F_000             1012
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.927
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         6891
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0675P)^2^+3.6755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1103
_refine_ls_wR_factor_ref         0.1143
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6219
_reflns_number_total             6891
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00678_si_001.cif
_cod_data_source_block           x1506011
_cod_database_code               4087886
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.267
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N48-C57 = N48-C59 = N48-C60 = N48-C58
 1.5 with sigma of 0.005
 N48-C49 = C50-C49 = N48-C53 = C54-C53 = N48-C51 = C52-C51 = N48-C55 = C56-C55
 1.5 with sigma of 0.005
 C55-C51 = C59-C58 = C59-C60
 2.2 with sigma of 0.005
3. Rigid bond restraints
 N48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: C49(0.75) H49A(0.75) H49B(0.75) C50(0.75) H50A(0.75) H50B(0.75)
 H50C(0.75) C51(0.75) H51A(0.75) H51B(0.75) C52(0.75) H52A(0.75) H52B(0.75)
 H52C(0.75) C53(0.75) H53A(0.75) H53B(0.75) C54(0.75) H54A(0.75) H54B(0.75)
 H54C(0.75) C55(0.75) H55A(0.75) H55B(0.75) C56(0.75) H56A(0.75) H56B(0.75)
 H56C(0.75) C57(0.25) H57A(0.25) H57B(0.25) H57C(0.25) C58(0.25) H58A(0.25)
 H58B(0.25) H58C(0.25) C59(0.25) H59A(0.25) H59B(0.25) H59C(0.25) C60(0.25)
 H60A(0.25) H60B(0.25) H60C(0.25)
5.a Riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B,H50C), C51(H51A,H51B), C52(H52A,H52B,H52C),
 C53(H53A,H53B), C54(H54A,H54B,H54C), C55(H55A,H55B), C56(H56A,H56B,H56C),
 C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C)
5.b Ternary CH refined with riding coordinates:
 B10(H10)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C8(H8), C14(H14), C21(H21), C28(H28)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C)
;
_shelx_res_checksum              49952
_shelx_hkl_checksum              60727
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'