Oxidation-induced ambiphilicity triggers N-N bond formation and dinitrogen release in octahedral terminal molybdenum(v) nitrido complexes.
Almquist, C. Christopher; Rajeshkumar, Thayalan; Jayaweera, H. D. A. Chathumal; Removski, Nicole; Zhou, Wen; Gelfand, Benjamin S.; Maron, Laurent; Piers, Warren E.; Chemical science 15 (2024) 5152–5162; doi:10.1039/d4sc00090k

data_1571035
_publ_section_title
;
 Oxidation-induced ambiphilicity triggers N-N bond formation and
 dinitrogen release in octahedral terminal molybdenum(v) nitrido
 complexes.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5152
_journal_page_last               5162
_journal_paper_doi               10.1039/d4sc00090k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C33 H36 B2 Mo N10, C2 F6 N O4 S2'
_chemical_formula_sum            'C35 H36 B2 F6 Mo N11 O4 S2'
_chemical_formula_weight         970.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-06-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.171(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1157(15)
_cell_length_b                   25.2386(19)
_cell_length_c                   12.3932(10)
_cell_measurement_reflns_used    9749
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.32
_cell_measurement_theta_min      2.99
_cell_volume                     4621.7(7)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.982
_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  0.0838
_diffrn_reflns_av_unetI/netI     0.0739
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            31599
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.637
_diffrn_reflns_theta_min         2.991
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.799
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1086 before and 0.0666 after correction.
The Ratio of minimum to maximum transmission is 0.7691.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_description       block
_exptl_crystal_F_000             1972
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.041
_refine_diff_density_max         2.573
_refine_diff_density_min         -1.925
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         9019
_refine_ls_number_restraints     318
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0868
_refine_ls_R_factor_gt           0.0569
_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^)+(0.1106P)^2^+0.7985P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1524
_refine_ls_wR_factor_ref         0.1914
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6436
_reflns_number_total             9019
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230616ca715_0ma_a_sq
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_database_code               1571035
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.860
_shelx_estimated_absorpt_t_min   0.435
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-C34 \\sim F1A-C34
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.04
 S1-F1 \\sim S1-F2 \\sim S1-F3 \\sim S1-F1A \\sim S1-F2A \\sim S1-F3A
 with sigma of 0.04
 F2-C34 \\sim F2A-C34
 with sigma of 0.02
 F3-C34 \\sim F3A-C34
 with sigma of 0.02
 F6-C35 \\sim F6A-C35
 with sigma of 0.02
 S2-F4 \\sim S2-F5 \\sim S2-F6 \\sim S2-F4A \\sim S2-F5A \\sim S2-F6A
 with sigma of 0.04
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.04
 F5-C35 \\sim F5A-C35
 with sigma of 0.02
 F4-C35 \\sim F4A-C35
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim C34: within 3A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A \\sim C35: within 3A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
4. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C21(H21),
  C23(H23), C27(H27), C29(H29), C31(H31)
5.b Idealised Me refined as rotating group:
 N10(H10A,H10B,H10C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              29554
_shelx_fab_checksum              59202
_olex2_submission_special_instructions 'No special instructions were received'