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_4087887
_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 H28 B N7 O W'
_chemical_formula_sum            'C20 H28 B N7 O W'
_chemical_formula_weight         577.15
_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     iterative
_audit_creation_date             2014-12-09
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                91.531(5)
_cell_angle_beta                 104.687(4)
_cell_angle_gamma                108.251(4)
_cell_formula_units_Z            2
_cell_length_a                   9.9474(6)
_cell_length_b                   10.1924(6)
_cell_length_c                   12.0642(8)
_cell_measurement_reflns_used    9954
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.03
_cell_measurement_theta_min      4.60
_cell_volume                     1116.15(13)
_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 0.969
_diffrn_measured_fraction_theta_max 0.961
_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  0.0872
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20272
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         70.130
_diffrn_reflns_theta_min         3.813
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.797
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.4674
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1307 before and 0.0909 after correction.
The Ratio of minimum to maximum transmission is 0.6205.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.717
_exptl_crystal_description       plate
_exptl_crystal_F_000             568
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and pentane by slow evaporation'
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.055
_refine_diff_density_max         2.711
_refine_diff_density_min         -2.050
_refine_diff_density_rms         0.203
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         4079
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0521
_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^)+(0.0948P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1347
_refine_ls_wR_factor_ref         0.1414
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3479
_reflns_number_total             4079
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00678_si_003.cif
_cod_data_source_block           x1412001
_cod_original_cell_volume        1116.15(12)
_cod_database_code               4087887
_shelx_estimated_absorpt_t_max   0.615
_shelx_estimated_absorpt_t_min   0.337
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 B15(H15)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C10(H10), C18(H18), C25(H25)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              65372
_shelx_hkl_checksum              13349
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 1417669200
_olex2_date_sample_submission    1417669200
_olex2_diffrn_ambient_temperature_device Kryoflex
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder paratone oil'
_olex2_submission_original_sample_id RJB-3-189
_olex2_submission_special_instructions 'No special instructions were received'