Migratory insertion of isocyanide into a ketenyl-tungsten bond as key step in cyclization reactions.
Timmermann, Christopher; Thiem, Paula; Wanitschke, Dominik; Hüttenschmidt, Mareike; Romischke, Johanna; Villinger, Alexander; Seidel, Wolfram W.; Chemical science 13 (2021) 123–132; doi:10.1039/d1sc06149f

data_1565570
_publ_section_title
;
 Migratory insertion of isocyanide into a ketenyl-tungsten bond as key
 step in cyclization reactions.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              123
_journal_page_last               132
_journal_paper_doi               10.1039/d1sc06149f
_journal_volume                  13
_journal_year                    2021
_chemical_formula_moiety         'C31 H40 B N7 O4 W, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C32.5 H43 B Cl3 N7 O4 W'
_chemical_formula_weight         896.75
_chemical_name_systematic
'[Di(carbonyl)-\k2-C,O-{3-(2,6-dimethylphenylamino)propan-3-ylidene-1-oate}-hydridotris(3,4,5-trimethylpyrazolyl)borato-tungsten(II)]'
_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
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2021-02-04 deposited with the CCDC.	2021-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                98.146(2)
_cell_angle_beta                 97.680(2)
_cell_angle_gamma                105.730(2)
_cell_formula_units_Z            2
_cell_length_a                   9.9415(5)
_cell_length_b                   11.0539(6)
_cell_length_c                   17.5643(9)
_cell_measurement_reflns_used    9675
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      30.31
_cell_measurement_theta_min      2.27
_cell_volume                     1808.92(16)
_computing_cell_refinement       'Bruker Apex V7.51A'
_computing_data_collection       'Bruker Apex V7.51A'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'ORTEP-3v2.01 (Farrugia, 1997)'
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      123(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 QUEST diffractometer'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0585
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            86328
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
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_diffrn_reflns_theta_max         31.998
_diffrn_reflns_theta_min         2.274
_diffrn_source                   'microfocus sealed tube'
_exptl_absorpt_coefficient_mu    3.462
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_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2014)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       needle
_exptl_crystal_F_000             898
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane/methanol'
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.060
_platon_squeeze_details
;
The unit cell contains three dichloromethane molecules which have been treated 
as a diffuse contribution to the overall scattering without specific atom 
positions by SQUEEZE/PLATON. These were removed from the model, but included 
in the empirical formula.
;
_refine_diff_density_max         2.039
_refine_diff_density_min         -1.687
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
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_refine_ls_number_reflns         12545
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0269P)^2^+1.6791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0641
_refine_ls_wR_factor_ref         0.0666
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10776
_reflns_number_total             12545
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06149f2.cif
_cod_data_source_block           is_ct1734
_cod_depositor_comments
'Adding full bibliography for 1565569--1565576.cif.'
_cod_original_formula_sum        'C32.50 H43 B Cl3 N7 O4 W'
_cod_database_code               1565570
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.377
_shelx_estimated_absorpt_t_max   0.819
_platon_squeeze_void_probe_radius 1.20
_shelx_res_checksum              24829
_shelx_hkl_checksum              93572