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_4087885
_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_absolute_configuration ad
_chemical_formula_moiety         'C39 H43 B N7 O W, 2(C4 H8 O), B F4'
_chemical_formula_sum            'C47 H59 B2 F4 N7 O3 W'
_chemical_formula_weight         1051.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7179(11)
_cell_length_b                   18.9078(17)
_cell_length_c                   19.0535(17)
_cell_measurement_reflns_used    9766
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.31
_cell_measurement_theta_min      3.29
_cell_volume                     4581.7(7)
_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 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0377
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            80497
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.427
_diffrn_reflns_theta_min         3.293
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.217
_exptl_absorpt_correction_T_max  0.6304
_exptl_absorpt_correction_T_min  0.4542
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0926 before and 0.0681 after correction.
The Ratio of minimum to maximum transmission is 0.7205.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       block
_exptl_crystal_F_000             2136
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.163
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 3746 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         9018
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0230
_refine_ls_R_factor_gt           0.0223
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0220P)^2^+3.0933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0520
_refine_ls_wR_factor_ref         0.0524
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                8821
_reflns_number_total             9018
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00678_si_002.cif
_cod_data_source_block           x1506003
_cod_database_code               4087885
_shelx_estimated_absorpt_t_max   0.483
_shelx_estimated_absorpt_t_min   0.361
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C66-C61 = C61-C62 = C63-C62 = C66-C65 = C63-C64 = C64-C65
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C66) = Uanis(C62)
Uanis(C65) = Uanis(C63)
Uanis(C63) = Uanis(C65)
4. Rigid body (RIGU) restrains
 O60, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H61C(0.5) H61D(0.5) H61A(0.5) H61B(0.5) C62(0.5) H62A(0.5)
 H62B(0.5) C63(0.5) H63A(0.5) H63B(0.5) H64A(0.5) H64B(0.5) H64C(0.5) H64D(0.5)
 C65(0.5) H65A(0.5) H65B(0.5) C66(0.5) H66A(0.5) H66B(0.5)
6.a Ternary CH refined with riding coordinates:
 B4(H4), C27(H27)
6.b Secondary CH2 refined with riding coordinates:
 C61(H61C,H61D), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,
 H64B), C64(H64C,H64D), C65(H65A,H65B), C66(H66A,H66B), C56(H56A,H56B),
 C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C15(H15), C20(H20), C24(H24), C25(H25), C31(H31), C32(H32), C33(H33),
 C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43),
  C44(H44), C45(H45), C46(H46), C47(H47)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              95274
_shelx_hkl_checksum              99121
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id RJB-4-43
_olex2_submission_special_instructions 'No special instructions were received'