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_1571032
_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
'Al C16 F36 O4, C65.5 H64.5 B4 Mo2 N20, 3(C7 H8), 0.5(C6 H6), 0.5(C7 H5)'
_chemical_formula_sum            'C109 H94 Al B4 F36 Mo2 N20 O4'
_chemical_formula_weight         2694.14
_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             2023-10-10
_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                109.516(4)
_cell_angle_beta                 91.769(4)
_cell_angle_gamma                114.335(4)
_cell_formula_units_Z            2
_cell_length_a                   16.5897(11)
_cell_length_b                   18.7404(12)
_cell_length_c                   24.0681(16)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.27
_cell_measurement_theta_min      2.80
_cell_volume                     6301.2(8)
_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 0.964
_diffrn_measured_fraction_theta_max 0.964
_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  0.0929
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            83381
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        66.591
_diffrn_reflns_theta_max         66.591
_diffrn_reflns_theta_min         2.981
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.668
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6572
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0879 before and 0.0694 after correction.
The Ratio of minimum to maximum transmission is 0.8721.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Orange
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       Block
_exptl_crystal_F_000             2722
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.037
_refine_diff_density_max         0.900
_refine_diff_density_min         -0.827
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1805
_refine_ls_number_reflns         21465
_refine_ls_number_restraints     906
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.1056
_refine_ls_R_factor_gt           0.0761
_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^)+(0.1440P)^2^+6.3563P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2083
_refine_ls_wR_factor_ref         0.2359
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15046
_reflns_number_total             21465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230608cj697orange_0m_a
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_database_code               1571032
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.648
_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
 C103-C101 = C103-C102 = C99-F38 = C100-C150 = C93-F40 = C98-F36
 1.4 with sigma of 0.02
 C26D-C31D = C30D-C29D
 1.4 with sigma of 0.02
 C151-C152 = C152-C153 = C153-C154 = C154-C67 = C67-C68
 1.4 with sigma of 0.01
 C70-C71 = C71-C72 = C72-C73 = C73-C74 = C74-C75
 1.4 with sigma of 0.01
3. Rigid bond restraints
 C70, C71, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F23 \\sim F24 \\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15
\\sim F16 \\sim F17 \\sim F18 \\sim F19 \\sim F20 \\sim F33 \\sim F37 \\sim F21
\\sim F35 \\sim F38 \\sim F22 \\sim F25 \\sim F26 \\sim F27 \\sim F28 \\sim F29
\\sim F30 \\sim F31 \\sim F32 \\sim F34 \\sim F39 \\sim F36 \\sim F40 \\sim F42
\\sim F41 \\sim F44 \\sim F45: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C101 \\sim C102 \\sim C103 \\sim C147 \\sim C148 \\sim C149: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C150 \\sim C100 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Mo1 \\sim Mo2 \\sim Mo2D \\sim Mo1D: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim
C26D \\sim C31D \\sim C30D \\sim C29D \\sim C33D \\sim C28D \\sim C32D \\sim
C27D: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
C92 \\sim C93 \\sim C99 \\sim C98: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
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(F23) \\sim Ueq, Uanis(F24) \\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(F19) \\sim Ueq, Uanis(F20)
\\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F21) \\sim Ueq,
Uanis(F35) \\sim Ueq, Uanis(F38) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F25)
\\sim Ueq, Uanis(F26) \\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(F28) \\sim Ueq,
Uanis(F29) \\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F31) \\sim Ueq, Uanis(F32)
\\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F39) \\sim Ueq, Uanis(F36) \\sim Ueq,
Uanis(F40) \\sim Ueq, Uanis(F42) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F44)
\\sim Ueq, Uanis(F45) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C57) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C98) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C150) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C104) \\sim Ueq,
Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C147) \\sim Ueq, Uanis(C148) \\sim Ueq,
Uanis(C149) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(F33) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F44)
\\sim Ueq, Uanis(F40) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(F45) \\sim Ueq,
Uanis(F41) \\sim Ueq, Uanis(F9) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C28D)=Sof(C27D)=Sof(H27D)=Sof(C26D)=Sof(C31D)=Sof(H31D)=Sof(C30D)=
 Sof(C33D)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C32D)=Sof(H32D)=Sof(H32E)=
 Sof(H32F)=Sof(C29D)=Sof(H29D)=1-FVAR(1)
 Sof(C26)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(C29)=Sof(H29)=Sof(C28)=Sof(C27)=
 Sof(H27)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C32)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=FVAR(1)
 Sof(F34)=Sof(F39)=Sof(F36)=1-FVAR(2)
 Sof(F33)=Sof(F37)=Sof(F21)=FVAR(2)
 Sof(F40)=Sof(F42)=Sof(F41)=1-FVAR(3)
 Sof(F23)=Sof(F24)=Sof(F10)=FVAR(3)
 Sof(F44)=Sof(F45)=1-FVAR(4)
 Sof(F38)=Sof(F22)=FVAR(4)
 Sof(Mo2D)=1-FVAR(5)
 Sof(Mo2)=FVAR(5)
 Sof(Mo1D)=1-FVAR(6)
 Sof(Mo1)=FVAR(6)
 Fixed Sof: C24(0.5) H24A(0.5) H24B(0.5) H24C(0.5) C101(0.5) H101(0.5)
 C102(0.5) H102(0.5) C103(0.5) H103(0.5) C147(0.5) H147(0.5) C148(0.5)
 H148(0.5) C149(0.5) H149(0.5) C100(0.5) C104(0.5) H104(0.5) C105(0.5)
 H105(0.5) C106(0.5) H106(0.5) C107(0.5) H107(0.5) C108(0.5) H108(0.5) C150(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C31(H31), C29(H29), C27(H27), C14(H14),
 C13(H13), C12(H12), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C7(H7),
  C6(H6), C37(H37), C36(H36), C35(H35), C19(H19), C21(H21), C23(H23), C44(H44),
 C43(H43), C42(H42), C45(H45), C46(H46), C47(H47), C39(H39), C40(H40), C41(H41),
  C50(H50), C49(H49), C48(H48), C60(H60), C62(H62), C64(H64), C56(H56),
 C54(H54), C52(H52), C152(H152), C153(H153), C154(H154), C67(H67), C68(H68),
 C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C78(H78), C79(H79), C80(H80),
  C81(H81), C82(H82), C101(H101), C102(H102), C103(H103), C147(H147),
 C148(H148), C149(H149), C104(H104), C105(H105), C106(H106), C107(H107),
 C108(H108), C8(H8), C27D(H27D), C31D(H31D), C29D(H29D)
6.b Fitted hexagon refined as free rotating group:
 C101(C102,C103,C147,C148,C149), C100(C104,C105,C106,C107,C108)
6.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C32(H32A,H32B,H32C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C58(H58A,H58B,H58C), C57(H57A,
 H57B,H57C), C69(H69A,H69B,H69C), C76(H76A,H76B,H76C), C83(H83A,H83B,H83C),
 C33D(H33D,H33E,H33F), C32D(H32D,H32E,H32F)
;
_shelx_res_checksum              28847
_olex2_submission_special_instructions 'No special instructions were received'