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_1571028
_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         'C35 H33 B2 F6 Mo N10 O4 S2'
_chemical_formula_sum            'C35 H33 B2 F6 Mo N10 O4 S2'
_chemical_formula_weight         953.39
_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             2023-06-20
_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                70.272(4)
_cell_angle_beta                 85.441(4)
_cell_angle_gamma                80.569(5)
_cell_formula_units_Z            2
_cell_length_a                   8.9517(7)
_cell_length_b                   15.7349(13)
_cell_length_c                   17.3073(13)
_cell_measurement_reflns_used    9776
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.35
_cell_measurement_theta_min      3.33
_cell_volume                     2262.9(3)
_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 0.963
_diffrn_measured_fraction_theta_max 0.963
_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  0.0704
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            39369
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        66.593
_diffrn_reflns_theta_max         66.593
_diffrn_reflns_theta_min         2.713
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.864
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.3928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1373 before and 0.0812 after correction.
The Ratio of minimum to maximum transmission is 0.5212.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       block
_exptl_crystal_F_000             966
_exptl_crystal_size_max          0.465
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.367
_refine_diff_density_min         -2.221
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     671
_refine_ls_number_reflns         7702
_refine_ls_number_restraints     1140
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0554
_refine_ls_R_factor_gt           0.0493
_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^)+(0.1048P)^2^+1.2587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1442
_refine_ls_wR_factor_ref         0.1530
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6795
_reflns_number_total             7702
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230619cj01148_0m_a_sq
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_database_code               1571028
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.267
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26A-B2 \\sim C26-B2
 with sigma of 0.02
 C32-C27 \\sim C32-C29 \\sim C32A-C27A \\sim C32A-C29A
 with sigma of 0.04
 B2-C27 \\sim B2-C31 \\sim B2-C27A \\sim B2-C31A
 with sigma of 0.04
 C33-C29 \\sim C33-C31 \\sim C33A-C29A \\sim C33A-C31A
 with sigma of 0.04
 C32A-C28A \\sim C32-C28
 with sigma of 0.02
 C33-C30 \\sim C33A-C30A
 with sigma of 0.02
 C25-C21 \\sim C25-C23 \\sim C25A-C21A \\sim C25A-C23A
 with sigma of 0.04
 C24-C19 \\sim C24-C21 \\sim C24A-C19A \\sim C24A-C21A
 with sigma of 0.04
 B1-C23 \\sim B1-C19 \\sim B1-C23A \\sim B1-C19A
 with sigma of 0.04
 C25A-C22A \\sim C25-C22
 with sigma of 0.02
 C18-B1 \\sim C18A-B1
 with sigma of 0.02
 C24-C20 \\sim C24A-C20A
 with sigma of 0.02
3. Restrained planarity
 C26A, C27A, C28A, C29A, C30A, C31A, C32A, C33A, B2
 with sigma of 0.1
 C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, B1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C26 \\sim C26A \\sim C27 \\sim C27A \\sim C28 \\sim C28A \\sim C29 \\sim C29A
\\sim C30 \\sim C30A \\sim C31 \\sim C31A \\sim C32 \\sim C32A \\sim C33 \\sim
C33A: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
C18 \\sim C18A \\sim C19 \\sim C19A \\sim C20 \\sim C20A \\sim C21 \\sim C21A
\\sim C22 \\sim C22A \\sim C23 \\sim C23A \\sim C24 \\sim C24A \\sim C25 \\sim
C25A: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
5. Others
 Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=
 Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(C26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(C31)=
 Sof(H31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=FVAR(1)
 Sof(C18A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=
 Sof(C19A)=Sof(H19A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=
 Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=FVAR(2)
6.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), C23A(H23A),
 C21A(H21A), C19A(H19A), C19(H19), C21(H21), C23(H23), C27A(H27A), C29A(H29A),
 C31A(H31A), C27(H27), C29(H29), C31(H31)
6.b Fitted hexagon refined as free rotating group:
 C18A(C23A,C22A,C21A,C20A,C19A), C26A(C27A,C28A,C29A,C30A,C31A)
6.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C25(H25A,H25B,H25C), C25A(H25D,
 H25E,H25F), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F), C33(H33A,H33B,H33C),
 C33A(H33D,H33E,H33F)
;
_shelx_res_checksum              25782
_shelx_fab_checksum              50215
_olex2_submission_special_instructions 'No special instructions were received'