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_1571037
_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
'4(C40 H38 B2 Mo N11), 4(Al C16 F36 O4), 7.833(C6 H12)'
_chemical_formula_sum            'C271 H246 Al4 B8 F144 Mo4 N44 O16'
_chemical_formula_weight         7689.26
_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             2023-10-12
_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                99.265(5)
_cell_angle_beta                 99.280(5)
_cell_angle_gamma                100.583(5)
_cell_formula_units_Z            1
_cell_length_a                   14.8333(10)
_cell_length_b                   17.3050(12)
_cell_length_c                   33.810(3)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      66.70
_cell_measurement_theta_min      2.65
_cell_volume                     8255.3(11)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.962
_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  0.2159
_diffrn_reflns_av_unetI/netI     0.1981
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            125145
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        66.594
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         2.649
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.620
_exptl_absorpt_correction_T_max  0.7079
_exptl_absorpt_correction_T_min  0.5107
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1608 before and 0.1201 after correction.
The Ratio of minimum to maximum transmission is 0.7214.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Purple
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       Plate
_exptl_crystal_F_000             3864
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.281
_refine_diff_density_min         -2.380
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2360
_refine_ls_number_reflns         28074
_refine_ls_number_restraints     991
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.1590
_refine_ls_R_factor_gt           0.1193
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1579P)^2^+15.6493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2886
_refine_ls_wR_factor_ref         0.3241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18462
_reflns_number_total             28074
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230221CA672_0m_a
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_original_cell_volume        8255.4(10)
_cod_database_code               1571037
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.437
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C213-C214 = C115-C125
 1.4 with sigma of 0.02
 C115-F74
 1.6 with sigma of 0.02
 C116-F76
 1.7 with sigma of 0.02
3. Rigid bond restraints
 C200, C201, C202, C203, C204, C205, C206, C207, C208, C209, C210, C211, C212,
 C213
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C214, C215, C216, C217, C218, C219, C220
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C114 \\sim C115 \\sim C117 \\sim C116 \\sim C81 \\sim C125: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C116 \\sim C81: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17
\\sim F18 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim F25
\\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim F31 \\sim F32 \\sim F33
\\sim F34 \\sim F35 \\sim F36 \\sim F37 \\sim F38 \\sim F39 \\sim F40 \\sim F41
\\sim F42 \\sim F43 \\sim F44 \\sim F45 \\sim F46 \\sim F47 \\sim F48 \\sim F49
\\sim F50 \\sim F51 \\sim F52 \\sim F53 \\sim F54 \\sim F55 \\sim F56 \\sim F57
\\sim F58 \\sim F59 \\sim F60 \\sim F61 \\sim F62 \\sim F63 \\sim F64 \\sim F65
\\sim F66 \\sim F67 \\sim F68 \\sim F69 \\sim F70 \\sim F71 \\sim F72 \\sim F79
\\sim F80 \\sim F81 \\sim F76 \\sim F77 \\sim F78 \\sim F73 \\sim F74 \\sim
F75: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C200) \\sim Ueq, Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C203) \\sim Ueq, Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq,
Uanis(C206) \\sim Ueq, Uanis(C207) \\sim Ueq, Uanis(C208) \\sim Ueq,
Uanis(C209) \\sim Ueq, Uanis(C210) \\sim Ueq, Uanis(C211) \\sim Ueq,
Uanis(C212) \\sim Ueq, Uanis(C213) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C214) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C216) \\sim Ueq,
Uanis(C217) \\sim Ueq, Uanis(C218) \\sim Ueq, Uanis(C219) \\sim Ueq,
Uanis(C220) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C124) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C108) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C127) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq,
Uanis(C41) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C114)
\\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C117) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O6) \\sim Ueq, Uanis(O8) \\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(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, Uanis(F28) \\sim Ueq, Uanis(F29)
\\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F31) \\sim Ueq, Uanis(F32) \\sim Ueq,
Uanis(F33) \\sim Ueq, Uanis(F34) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F36)
\\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F38) \\sim Ueq, Uanis(F39) \\sim Ueq,
Uanis(F40) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F42) \\sim Ueq, Uanis(F43)
\\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F45) \\sim Ueq, Uanis(F46) \\sim Ueq,
Uanis(F47) \\sim Ueq, Uanis(F48) \\sim Ueq, Uanis(F49) \\sim Ueq, Uanis(F50)
\\sim Ueq, Uanis(F51) \\sim Ueq, Uanis(F52) \\sim Ueq, Uanis(F53) \\sim Ueq,
Uanis(F54) \\sim Ueq, Uanis(F55) \\sim Ueq, Uanis(F56) \\sim Ueq, Uanis(F57)
\\sim Ueq, Uanis(F58) \\sim Ueq, Uanis(F59) \\sim Ueq, Uanis(F60) \\sim Ueq,
Uanis(F61) \\sim Ueq, Uanis(F62) \\sim Ueq, Uanis(F63) \\sim Ueq, Uanis(F64)
\\sim Ueq, Uanis(F65) \\sim Ueq, Uanis(F66) \\sim Ueq, Uanis(F67) \\sim Ueq,
Uanis(F68) \\sim Ueq, Uanis(F69) \\sim Ueq, Uanis(F70) \\sim Ueq, Uanis(F71)
\\sim Ueq, Uanis(F72) \\sim Ueq, Uanis(F79) \\sim Ueq, Uanis(F80) \\sim Ueq,
Uanis(F81) \\sim Ueq, Uanis(F76) \\sim Ueq, Uanis(F77) \\sim Ueq, Uanis(F78)
\\sim Ueq, Uanis(F73) \\sim Ueq, Uanis(F74) \\sim Ueq, Uanis(F75) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C115)=Sof(F73)=Sof(F74)=Sof(F75)=1-FVAR(1)
 Sof(C114)=Sof(F61)=Sof(F62)=Sof(F63)=FVAR(1)
 Sof(C116)=Sof(F76)=Sof(F77)=Sof(F78)=1-FVAR(2)
 Sof(C81)=Sof(F55)=Sof(F56)=Sof(F57)=FVAR(2)
 Sof(C117)=Sof(F79)=Sof(F80)=Sof(F81)=1-FVAR(3)
 Sof(C124)=Sof(F58)=Sof(F59)=Sof(F60)=FVAR(3)
 Fixed Sof: H80A(0.5) H80B(0.5) H80C(0.5) H80D(0.5) H80E(0.5) H80F(0.5)
 C200(0.5) H20A(0.5) H20B(0.5) C201(0.5) H20C(0.5) H20D(0.5) C202(0.5)
 H20E(0.5) H20F(0.5) C203(0.5) H20G(0.5) H20H(0.5) C204(0.5) H20I(0.5)
 H20J(0.5) C205(0.5) H20K(0.5) H20L(0.5) C206(0.5) H20M(0.5) H20N(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C94(H94A,H94B), C109(H10A,H10B), C110(H11A,H11B), C111(H11C,H11D), C112(H11E,
 H11F), C113(H11G,H11H), C200(H20A,H20B), C201(H20C,H20D), C202(H20E,H20F),
 C203(H20G,H20H), C204(H20I,H20J), C205(H20K,H20L), C206(H20M,H20N), C207(H20O,
 H20P), C208(H20Q,H20R), C209(H20S,H20T), C210(H21A,H21B), C211(H21C,H21D),
 C212(H21E,H21F), C213(H21G,H21H), C214(H21I,H21J), C215(H21K,H21L), C216(H21M,
 H21N), C217(H21O,H21P), C218(H21Q,H21R), C219(H21S,H21T), C220(H22A,H22B)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C6(H6), C7(H7), C8(H8), C23(H23), C22(H22),
 C20(H20), C19(H19), C2(H2), C3(H3), C4(H4), C26(H26), C27(H27), C29(H29),
 C30(H30), C17(H17), C16(H16), C15(H15), C14(H14), C13(H13), C12(H12), C37(H37),
  C36(H36), C35(H35), C46(H46), C47(H47), C48(H48), C51(H51), C50(H50),
 C49(H49), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57), C70(H70),
  C69(H69), C67(H67), C66(H66), C44(H44), C43(H43), C42(H42), C63(H63),
 C62(H62), C60(H60), C59(H59), C75(H75), C76(H76), C77(H77)
6.c Disordered Me refined with riding coordinates:
 C80(H80A,H80B,H80C,H80D,H80E,H80F)
6.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), C39(H39A,H39B,H39C), C40(H40A,H40B,
 H40C), C71(H71A,H71B,H71C), C64(H64A,H64B,H64C), C79(H79A,H79B,H79C)
;
_shelx_res_checksum              59819
_olex2_submission_special_instructions 'No special instructions were received'