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_1571029
_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         'C62 H58 B4 Mo2 N19, C2 F6 N O4 S2, 2.5(C7 H8)'
_chemical_formula_sum            'C81.5 H78 B4 F6 Mo2 N20 O4 S2'
_chemical_formula_weight         1814.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.386(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5414(8)
_cell_length_b                   23.6171(10)
_cell_length_c                   20.4202(9)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    173
_cell_measurement_theta_max      72.486
_cell_measurement_theta_min      2.861
_cell_volume                     8459.4(6)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_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  0.0666
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            49469
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         3.310
_diffrn_source_current           0.64
_diffrn_source_power             0.028576
_diffrn_source_voltage           44.65
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.516
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5575
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0770 before and 0.0472 after correction.
The Ratio of minimum to maximum transmission is 0.7398.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       plate
_exptl_crystal_F_000             3716
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.616
_refine_diff_density_min         -1.249
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1532
_refine_ls_number_reflns         14457
_refine_ls_number_restraints     4929
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0992
_refine_ls_R_factor_gt           0.0658
_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^)+(0.0882P)^2^+13.9977P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1663
_refine_ls_wR_factor_ref         0.1875
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9955
_reflns_number_total             14457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           ca02-293
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_original_formula_sum        'C81.50 H78 B4 F6 Mo2 N20 O4 S2'
_cod_database_code               1571029
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.458
_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
 C1S_1-C2S_1
 C1S_2-C2S_2
 C1S_3-C2S_3
 C1S_4-C2S_4
 C1S_5-C2S_5
 C1S_6-C2S_6
 with sigma of 0.02
 C25A-B1 \\sim C25-B1 \\sim C18A-B2 \\sim C18-B2 \\sim C56A-B3 \\sim C56-B3
\\sim C49A-B4 \\sim C49-B4
 with sigma of 0.02
 C1S_1-C3S_1 \\sim C1S_1-C7S_1
 C1S_2-C3S_2 \\sim C1S_2-C7S_2
 C1S_3-C3S_3 \\sim C1S_3-C7S_3
 C1S_4-C3S_4 \\sim C1S_4-C7S_4
 C1S_5-C3S_5 \\sim C1S_5-C7S_5
 C1S_6-C3S_6 \\sim C1S_6-C7S_6
 with sigma of 0.02
 C31A-C28A \\sim C31-C28 \\sim C24A-C21A \\sim C24-C21 \\sim C62A-C59A \\sim
C62-C59 \\sim C55A-C52A ~
 C55-C52
 with sigma of 0.02
 N1X_7-S1X_7 \\sim N1X_7-S1X_7
 N1X_8-S1X_8 \\sim N1X_8-S1X_8
 with sigma of 0.02
 S1X_7-O1X_7 \\sim S1X_7-O2X_7 \\sim S2X_7-O3X_7 \\sim S2X_7-O4X_7
 S1X_8-O1X_8 \\sim S1X_8-O2X_8 \\sim S2X_8-O3X_8 \\sim S2X_8-O4X_8
 with sigma of 0.02
 S1X_7-C1X_7 \\sim S2X_7-C2X_7
 S1X_8-C1X_8 \\sim S2X_8-C2X_8
 with sigma of 0.02
 C1X_7-F1X_7 \\sim C1X_7-F2X_7 \\sim C1X_7-F3X_7 \\sim C2X_7-F4X_7 \\sim
C2X_7-F5X_7 \\sim C2X_7-
 F6X_7
 C1X_8-F1X_8 \\sim C1X_8-F2X_8 \\sim C1X_8-F3X_8 \\sim C2X_8-F4X_8 \\sim
C2X_8-F5X_8 \\sim C2X_8-
 F6X_8
 with sigma of 0.02
 N1X_7-O1X_7 \\sim N1X_7-O2X_7 \\sim N1X_7-O3X_7 \\sim N1X_7-O4X_7
 N1X_8-O1X_8 \\sim N1X_8-O2X_8 \\sim N1X_8-O3X_8 \\sim N1X_8-O4X_8
 with sigma of 0.04
 N1X_7-C1X_7 \\sim N1X_7-C2X_7
 N1X_8-C1X_8 \\sim N1X_8-C2X_8
 with sigma of 0.04
 S1X_7-F1X_7 \\sim S1X_7-F2X_7 \\sim S1X_7-F3X_7 \\sim S2X_7-F4X_7 \\sim
S2X_7-F5X_7 \\sim S2X_7-
 F6X_7
 S1X_8-F1X_8 \\sim S1X_8-F2X_8 \\sim S1X_8-F3X_8 \\sim S2X_8-F4X_8 \\sim
S2X_8-F5X_8 \\sim S2X_8-
 F6X_8
 with sigma of 0.04
 S1X_7-S2X_7
 S1X_8-S2X_8
 with sigma of 0.04
 O1X_7-O2X_7 \\sim O3X_7-O4X_7
 O1X_8-O2X_8 \\sim O3X_8-O4X_8
 with sigma of 0.04
 F1X_7-F2X_7 \\sim F2X_7-F3X_7 \\sim F3X_7-F1X_7 \\sim F4X_7-F5X_7 \\sim
F5X_7-F6X_7 \\sim F6X_7-
 F4X_7
 F1X_8-F2X_8 \\sim F2X_8-F3X_8 \\sim F3X_8-F1X_8 \\sim F4X_8-F5X_8 \\sim
F5X_8-F6X_8 \\sim F6X_8-
 F4X_8
 with sigma of 0.04
 C1X_7-O1X_7 \\sim C1X_7-O2X_7 \\sim C2X_7-O3X_7 \\sim C2X_7-O4X_7
 C1X_8-O1X_8 \\sim C1X_8-O2X_8 \\sim C2X_8-O3X_8 \\sim C2X_8-O4X_8
 with sigma of 0.04
3. Restrained planarity
 C1S_1, C2S_1, C3S_1, C4S_1, C5S_1, C6S_1, C7S_1
 C1S_2, C2S_2, C3S_2, C4S_2, C5S_2, C6S_2, C7S_2
 C1S_3, C2S_3, C3S_3, C4S_3, C5S_3, C6S_3, C7S_3
 C1S_4, C2S_4, C3S_4, C4S_4, C5S_4, C6S_4, C7S_4
 C1S_5, C2S_5, C3S_5, C4S_5, C5S_5, C6S_5, C7S_5
 C1S_6, C2S_6, C3S_6, C4S_6, C5S_6, C6S_6, C7S_6
 with sigma of 0.1
 C49, C50, C51, C52, C53, C54, C55, B4
 with sigma of 0.1
 C56, C61, C59, C57, C58, C62, C60, B3
 with sigma of 0.1
 C18A, C23A, C22A, C21A, C20A, C19A, C24A, B2
 with sigma of 0.1
 C49A, C50A, C51A, C52A, C53A, C54A, C55A, B4
 with sigma of 0.1
 C56A, C61A, C60A, C59A, C58A, C57A, C62A, B3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C25 \\sim C30 \\sim C29 \\sim C28 \\sim C27 \\sim C26 \\sim C25A \\sim C30A
\\sim C29A \\sim C28A \\sim C27A \\sim C26A \\sim C31 \\sim C31A: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C18 \\sim C23 \\sim C22 \\sim C21 \\sim C20 \\sim C19 \\sim C18A \\sim C23A
\\sim C22A \\sim C21A \\sim C20A \\sim C19A \\sim C24 \\sim C24A: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C56 \\sim C61 \\sim C60 \\sim C59 \\sim C57 \\sim C58 \\sim C56A \\sim C61A
\\sim C60A \\sim C59A \\sim C58A \\sim C57A \\sim C62 \\sim C62A: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C49A \\sim C50A
\\sim C51A \\sim C52A \\sim C53A \\sim C54A \\sim C55 \\sim C55A: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C4S_2 \\sim C1S_2 \\sim C2S_2 \\sim C3S_2 \\sim C7S_2 \\sim C6S_2 \\sim C5S_2
\\sim C3S_1 \\sim C1S_1 \\sim C2S_1 \\sim C7S_1 \\sim C4S_1 \\sim C6S_1 \\sim
C5S_1: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
C6S_5 \\sim C1S_5 \\sim C2S_5 \\sim C3S_5 \\sim C7S_5 \\sim C4S_5 \\sim C5S_5
\\sim C4S_6 \\sim C1S_6 \\sim C2S_6 \\sim C3S_6 \\sim C7S_6 \\sim C6S_6 \\sim
C5S_6: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
C1S_3 \\sim C2S_3 \\sim C3S_3 \\sim C7S_3 \\sim C4S_3 \\sim C6S_3 \\sim C5S_3
\\sim C6S_4 \\sim C1S_4 \\sim C2S_4 \\sim C3S_4 \\sim C7S_4 \\sim C4S_4 \\sim
C5S_4: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3A
: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
: within 3A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 3A
: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
5. Same fragment restrains
{S1X_8, S2X_8, F1X_8, F2X_8, F3X_8, F4X_8, F5X_8, F6X_8, O1X_8, O2X_8, O3X_8,
O4X_8, N1X_8, C1X_8, C2X_8}
as
{S1X_7, S2X_7, F1X_7, F2X_7, F3X_7, F4X_7, F5X_7, F6X_7, O1X_7, O2X_7, O3X_7,
O4X_7, N1X_7, C1X_7, C2X_7} sigma for 1-2: 0.02 1-3: 0.04
6. Others
 Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(C53A)=
 Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=1-FVAR(1)
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(C53)=Sof(H53)=
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(1)
 Sof(C25A)=Sof(C30A)=Sof(H30A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(C27A)=
 Sof(H27A)=Sof(C26A)=Sof(H26A)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(2)
 Sof(C25)=Sof(C30)=Sof(H30)=Sof(C29)=Sof(H29)=Sof(C28)=Sof(C27)=Sof(H27)=
 Sof(C26)=Sof(H26)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(2)
 Sof(C18A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(C20A)=
 Sof(H20A)=Sof(C19A)=Sof(H19A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(3)
 Sof(C18)=Sof(C23)=Sof(H23)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(C20)=Sof(H20)=
 Sof(C19)=Sof(H19)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(3)
 Sof(C56A)=Sof(C61A)=Sof(H61A)=Sof(C60A)=Sof(H60A)=Sof(C59A)=Sof(C58A)=
 Sof(H58A)=Sof(C57A)=Sof(H57A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=1-FVAR(4)
 Sof(C56)=Sof(C61)=Sof(H61)=Sof(C60)=Sof(H60)=Sof(C59)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(4)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=1-FVAR(5)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=FVAR(5)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=1-FVAR(6)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=FVAR(6)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=0.5*(1-FVAR(8))
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(C3S)=Sof(H3S)=Sof(C4S)=
 Sof(H4S)=Sof(C5S)=Sof(H5S)=Sof(C6S)=Sof(H6S)=Sof(C7S)=Sof(H7S)=0.5*FVAR(8)
 Sof(S1X)=Sof(S2X)=Sof(F1X)=Sof(F2X)=Sof(F3X)=Sof(F4X)=Sof(F5X)=Sof(F6X)=
 Sof(O1X)=Sof(O2X)=Sof(O3X)=Sof(O4X)=Sof(N1X)=Sof(C1X)=Sof(C2X)=1-FVAR(8)
 Sof(S1X)=Sof(S2X)=Sof(F1X)=Sof(F2X)=Sof(F3X)=Sof(F4X)=Sof(F5X)=Sof(F6X)=
 Sof(O1X)=Sof(O2X)=Sof(O3X)=Sof(O4X)=Sof(N1X)=Sof(C1X)=Sof(C2X)=FVAR(8)
7.a Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC), C1S(H1SA,H1SB,H1SC), C1S(H1SA,H1SB,H1SC), C1S(H1SA,H1SB,
 H1SC), C1S(H1SA,H1SB,H1SC), C1S(H1SA,H1SB,H1SC)
7.b 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), C23(H23), C22(H22),
  C20(H20), C19(H19), C23A(H23A), C22A(H22A), C20A(H20A), C19A(H19A), C30(H30),
 C29(H29), C27(H27), C26(H26), C30A(H30A), C29A(H29A), C27A(H27A), C26A(H26A),
 C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
 C50(H50), C51(H51), C53(H53), C54(H54), C50A(H50A), C51A(H51A), C53A(H53A),
 C54A(H54A), C61(H61), C60(H60), C57(H57), C58(H58), C61A(H61A), C60A(H60A),
 C58A(H58A), C57A(H57A), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S),
 C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S), C3S(H3S), C4S(H4S), C5S(H5S),
  C6S(H6S), C7S(H7S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S),
 C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S), C3S(H3S), C4S(H4S), C5S(H5S),
  C6S(H6S), C7S(H7S)
7.c Fitted hexagon refined as free rotating group:
 C18(C23,C22,C21,C20,C19), C18A(C23A,C22A,C21A,C20A,C19A), C25(C30,C29,C28,C27,
 C26), C25A(C30A,C29A,C28A,C27A,C26A), C49(C50,C51,C52,C53,C54), C49A(C50A,C51A,
 C52A,C53A,C54A), C56(C61,C60,C59,C57,C58), C56A(C61A,C60A,C59A,C58A,C57A),
 C2S(C3S,C4S,C5S,C6S,C7S), C2S(C3S,C4S,C5S,C6S,C7S), C2S(C3S,C4S,C5S,C6S,C7S),
 C2S(C3S,C4S,C5S,C6S,C7S), C2S(C3S,C4S,C5S,C6S,C7S), C2S(C3S,C4S,C5S,C6S,C7S)
7.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C31(H31A,H31B,H31C), C31A(H31D,
 H31E,H31F), C55(H55A,H55B,H55C), C55A(H55D,H55E,H55F), C62(H62A,H62B,H62C),
 C62A(H62D,H62E,H62F)
;
_shelx_res_checksum              50303
_olex2_submission_special_instructions 'No special instructions were received'