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_1571026
_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         'C33 H34.996 B2 Li N9 O0.498, C5 H10 O'
_chemical_formula_sum            'C38 H45.01 B2 Li N9 O1.5'
_chemical_formula_weight         680.48
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2023-09-01
_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                105.8850(10)
_cell_angle_beta                 98.659(2)
_cell_angle_gamma                93.937(2)
_cell_formula_units_Z            2
_cell_length_a                   9.4559(2)
_cell_length_b                   13.3234(2)
_cell_length_c                   15.6012(4)
_cell_measurement_reflns_used    9760
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.35
_cell_measurement_theta_min      2.99
_cell_volume                     1856.39(7)
_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    'SHELXS  (Sheldrick, 2008)'
_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  0.0350
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            25840
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        66.591
_diffrn_reflns_theta_max         66.591
_diffrn_reflns_theta_min         2.992
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.598
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1058 before and 0.0537 after correction.
The Ratio of minimum to maximum transmission is 0.8887.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             722
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.241
_exptl_crystal_size_min          0.092
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         6326
_refine_ls_number_restraints     620
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0763
_refine_ls_R_factor_gt           0.0701
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0924P)^2^+1.9125P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1867
_refine_ls_wR_factor_ref         0.1929
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5603
_reflns_number_total             6326
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           cu_20230831ca57_0m_a
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_original_formula_sum        'C38 H45.01 B2 Li N9 O1.50'
_cod_database_code               1571026
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 N3A-B1 \\sim N3-B1
 with sigma of 0.02
 B1-N2 \\sim B1-N2A
 with sigma of 0.04
 B1-C8 \\sim B1-C8A
 with sigma of 0.04
 O1T-C5T \\sim O1S-C5S
 with sigma of 0.04
 C2T-C5T \\sim C2S-C5S
 with sigma of 0.04
3. Restrained planarity
 N2A, N3A, C6A, C7A, C8A, B1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N2 \\sim N3 \\sim C6 \\sim C7 \\sim C8 \\sim N2A \\sim N3A \\sim C6A \\sim C7A
\\sim C8A: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 3A
O1S \\sim O1T \\sim C1T \\sim C2T \\sim C3T \\sim C4T \\sim C5T \\sim C1S \\sim
C2S \\sim C3S \\sim C4S \\sim C5S: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
5. Others
 Sof(O1T)=Sof(C1T)=Sof(H1T)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(C3T)=Sof(H3TA)=
 Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=Sof(C5T)=Sof(H5TA)=Sof(H5TB)=Sof(H5TC)=
 Sof(N3A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=Sof(N2A)=1-
 FVAR(1)
 Sof(O1)=Sof(H1A)=Sof(H1B)=Sof(O1S)=Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2SA)=
 Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(N3)=
 Sof(C8)=Sof(H8)=Sof(C7)=Sof(H7)=Sof(C6)=Sof(H6)=Sof(N2)=Sof(C5S)=Sof(H5SA)=
 Sof(H5SB)=Sof(H5SC)=FVAR(1)
6.a Rotating group:
 O1(H1A,H1B)
6.b Ternary CH refined with riding coordinates:
 C1S(H1S), C1T(H1T)
6.c Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C2T(H2TA,H2TB), C3T(H3TA,
 H3TB), C4T(H4TA,H4TB)
6.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C8A(H8A), C7A(H7A), C6A(H6A), C8(H8), C7(H7), C6(H6), C2(H2), C3(H3),
 C4(H4), C9(H9), C10(H10), C11(H11), C13(H13), C15(H15), C17(H17), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C27(H27), C29(H29), C31(H31)
6.e Fitted pentagon refined as free rotating group:
 O1S(C1S,C2S,C3S,C4S), N3A(C8A,C7A,C6A,N2A), N3(C8,C7,C6,N2)
6.f Idealised Me refined as rotating group:
 C5T(H5TA,H5TB,H5TC), C5S(H5SA,H5SB,H5SC), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              77798
_olex2_submission_special_instructions 'No special instructions were received'