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_4087884
_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         'C22 H33 B N7 O W, C F3 O3 S'
_chemical_formula_sum            'C23 H33 B F3 N7 O4 S W'
_chemical_formula_weight         755.28
_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
_audit_creation_date             2015-10-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                82.414(3)
_cell_angle_beta                 84.135(4)
_cell_angle_gamma                89.855(3)
_cell_formula_units_Z            2
_cell_length_a                   8.0823(6)
_cell_length_b                   12.4028(8)
_cell_length_c                   14.5630(10)
_cell_measurement_reflns_used    9878
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.13
_cell_measurement_theta_min      3.08
_cell_volume                     1439.40(17)
_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      100.15
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.967
_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  0.0274
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18550
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.157
_diffrn_reflns_theta_min         3.077
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.659
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.4560
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0491 before and 0.0367 after correction.
The Ratio of minimum to maximum transmission is 0.4560.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.743
_exptl_crystal_description       plate
_exptl_crystal_F_000             748
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.019
_refine_diff_density_max         1.467
_refine_diff_density_min         -0.780
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         5286
_refine_ls_number_restraints     258
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0450P)^2^+3.0521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0848
_refine_ls_wR_factor_ref         0.0858
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5057
_reflns_number_total             5286
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00678_si_005.cif
_cod_data_source_block           x1509011
_cod_database_code               4087884
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.280
_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. Uiso/Uaniso restraints and constraints
N6 \\sim C9 \\sim C9A \\sim C10 \\sim C10A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
S101 \\sim O102 \\sim O103 \\sim O104 \\sim C105 \\sim F106 \\sim F107 \\sim
F108 \\sim S201 \\sim O202 \\sim O203 \\sim O204 \\sim C205 \\sim F206 \\sim
F207 \\sim F208: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
3. Others
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(S201)=Sof(O202)=Sof(O203)=Sof(O204)=Sof(C205)=Sof(F206)=Sof(F207)=
 Sof(F208)=1-FVAR(2)
 Sof(S101)=Sof(O102)=Sof(O103)=Sof(O104)=Sof(C105)=Sof(F106)=Sof(F107)=
 Sof(F108)=FVAR(2)
4.a Free rotating group:
 S101(O102,O103,O104,C105,F106,F107,F108), S201(O202,O203,O204,C205,F206,F207,
 F208)
4.b Ternary CH refined with riding coordinates:
 B32(H32)
4.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9A(H9AA,H9AB)
4.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C14(H14), C22(H22), C28(H28)
4.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              51949
_shelx_hkl_checksum              67745
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'