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_1571036
_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         'C66 H66 B4 Mo2 N19, Al C16 F36 O4, C2'
_chemical_formula_sum            'C84 H66 Al B4 F36 Mo2 N19 O4'
_chemical_formula_weight         2351.65
_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             2023-10-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                116.155(2)
_cell_angle_beta                 90.495(2)
_cell_angle_gamma                98.658(2)
_cell_formula_units_Z            2
_cell_length_a                   15.9395(9)
_cell_length_b                   18.5574(8)
_cell_length_c                   18.9383(9)
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.46
_cell_measurement_theta_min      2.69
_cell_volume                     4953.2(4)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.965
_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  0.0576
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            78183
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         2.788
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.295
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6119
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1093 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.8120.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.577
_exptl_crystal_description       Block
_exptl_crystal_F_000             2352
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.092
_refine_diff_density_max         2.931
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1661
_refine_ls_number_reflns         16877
_refine_ls_number_restraints     729
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0851P)^2^+9.3087P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1453
_refine_ls_wR_factor_ref         0.1559
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14151
_reflns_number_total             16877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230921ca749b_0ma_a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1571025--1571037.cif.
;
_cod_database_code               1571036
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.751
_shelx_estimated_absorpt_t_min   0.603
_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
 C71-C74 = C71-C73
 1.586 with sigma of 0.02
 F33-C81
 1.387 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C83 \\sim C84 \\sim C85 \\sim C83D \\sim C84D: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C25 \\sim C25D \\sim C19 \\sim C20 \\sim C21 \\sim C19D \\sim C20D \\sim C21D:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C74 \\sim C72 \\sim C73 \\sim C74D \\sim C72D \\sim C73D: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
F31 \\sim F31D \\sim F33 \\sim F33D: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C76 \\sim C77 \\sim C78 \\sim C76D \\sim C77D \\sim C78D: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim F25 \\sim F26 \\sim
F27: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
F19D \\sim F20D \\sim F21D \\sim F22D \\sim F23D \\sim F24D \\sim F25D \\sim
F26D \\sim F27D: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C83D)
\\sim Ueq, Uanis(C84D) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C25) \\sim Ueq, Uanis(C25D) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C19D) \\sim Ueq, Uanis(C20D) \\sim Ueq,
Uanis(C21D) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C74) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74D)
\\sim Ueq, Uanis(C72D) \\sim Ueq, Uanis(C73D) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8)
\\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq,
Uanis(F10D) \\sim Ueq, Uanis(F11D) \\sim Ueq, Uanis(F12D) \\sim Ueq,
Uanis(F13D) \\sim Ueq, Uanis(F14D) \\sim Ueq, Uanis(F15D) \\sim Ueq,
Uanis(F16D) \\sim Ueq, Uanis(F17D) \\sim Ueq, Uanis(F18D) \\sim Ueq, Uanis(F28)
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F33) \\sim Ueq,
Uanis(F31) \\sim Ueq, Uanis(F31D) \\sim Ueq, Uanis(F33D) \\sim Ueq, Uanis(F32)
\\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F36) \\sim Ueq,
Uanis(F19D) \\sim Ueq, Uanis(F20D) \\sim Ueq, Uanis(F21D) \\sim Ueq,
Uanis(F22D) \\sim Ueq, Uanis(F23D) \\sim Ueq, Uanis(F24D) \\sim Ueq,
Uanis(F25D) \\sim Ueq, Uanis(F26D) \\sim Ueq, Uanis(F27D) \\sim Ueq, Uanis(F19)
\\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq,
Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(F26)
\\sim Ueq, Uanis(F27) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C76D)
\\sim Ueq, Uanis(C77D) \\sim Ueq, Uanis(C78D) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(C19D)=Sof(H19D)=Sof(C20D)=Sof(C21D)=Sof(H21D)=Sof(C25D)=Sof(H25D)=
 Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=FVAR(1)
 Sof(C72D)=Sof(C73D)=Sof(C74D)=Sof(F10D)=Sof(F11D)=Sof(F12D)=Sof(F13D)=
 Sof(F14D)=Sof(F15D)=Sof(F16D)=Sof(F17D)=Sof(F18D)=1-FVAR(2)
 Sof(C72)=Sof(C73)=Sof(C74)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=
 Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
 Sof(F31D)=Sof(F33D)=1-FVAR(3)
 Sof(F33)=Sof(F31)=FVAR(3)
 Sof(C76D)=Sof(C77D)=Sof(C78D)=Sof(F19D)=Sof(F20D)=Sof(F21D)=Sof(F22D)=
 Sof(F23D)=Sof(F24D)=Sof(F25D)=Sof(F26D)=Sof(F27D)=1-FVAR(4)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F25)=Sof(F26)=
 Sof(F27)=Sof(C76)=Sof(C77)=Sof(C78)=FVAR(4)
 Fixed Sof: C83D(0.25) C84D(0.25) C84(0.5) C83(0.5) C85(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C6(H6), C7(H7), C8(H8),
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C23(H23), C20(H20),
  C21(H21), C19D(H19D), C21D(H21D), C27(H27), C29(H29), C31(H31), C35(H35),
 C36(H36), C37(H37), C42(H42), C43(H43), C44(H44), C39(H39), C40(H40), C41(H41),
  C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C52(H52),
 C54(H54), C56(H56), C60(H60), C62(H62), C64(H64)
5.b Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C25D(H25D,H25E,H25F), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C)
;
_shelx_res_checksum              48288
_olex2_submission_special_instructions 'No special instructions were received'