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_4087888
_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         'C20 H27 B N7 O W, B F4, C H2 Cl2'
_chemical_formula_sum            'C21 H29 B2 Cl2 F4 N7 O W'
_chemical_formula_weight         747.88
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                69.1200(10)
_cell_angle_beta                 76.6510(10)
_cell_angle_gamma                65.4140(10)
_cell_formula_units_Z            2
_cell_length_a                   11.4940(2)
_cell_length_b                   11.7784(2)
_cell_length_c                   12.1042(2)
_cell_measurement_reflns_used    9840
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.08
_cell_measurement_theta_min      3.93
_cell_volume                     1385.66(4)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.971
_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  0.0378
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            34589
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.074
_diffrn_reflns_theta_min         3.927
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.999
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.2717
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0644 before and 0.0474 after correction.
The Ratio of minimum to maximum transmission is 0.2717.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.792
_exptl_crystal_description       plate
_exptl_crystal_F_000             732
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.038
_refine_diff_density_max         2.053
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     350
_refine_ls_number_reflns         5118
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0249
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0309P)^2^+2.2246P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0615
_refine_ls_wR_factor_ref         0.0621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4918
_reflns_number_total             5118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00678_si_004.cif
_cod_data_source_block           x1509003
_cod_database_code               4087888
_shelx_estimated_absorpt_t_max   0.702
_shelx_estimated_absorpt_t_min   0.194
_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.a Ternary CH refined with riding coordinates:
 B9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C13(H13), C20(H20), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              61296
_shelx_hkl_checksum              975
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'