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_1571031
_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         'C2 Cl2.25, C33 H33 B2 Cl Mo N9'
_chemical_formula_sum            'C35 H37 B2 Cl3.25 Mo N9'
_chemical_formula_weight         816.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-10-03
_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                90
_cell_angle_beta                 110.709(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.601(3)
_cell_length_b                   19.921(4)
_cell_length_c                   12.437(3)
_cell_measurement_reflns_used    8241
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      28.24
_cell_measurement_theta_min      2.69
_cell_volume                     3615.5(13)
_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 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0657
_diffrn_reflns_av_unetI/netI     0.0607
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            18503
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.327
_diffrn_reflns_theta_min         2.045
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.644
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6797
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0735 before and 0.0667 after correction.
The Ratio of minimum to maximum transmission is 0.9115.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       Block
_exptl_crystal_F_000             1669
_exptl_crystal_size_max          0.292
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         4607
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0607
_refine_ls_R_factor_gt           0.0447
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0535P)^2^+4.5831P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3683
_reflns_number_total             4607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00090k2.cif
_cod_data_source_block           mo_20230629CJ01153_0m_a
_cod_depositor_comments
'Adding full bibliography for 1571025--1571037.cif.'
_cod_original_cell_volume        3615.6(14)
_cod_database_code               1571031
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.834
_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
 C20-Cl2 = C20-Cl3
 1.8 with sigma of 0.02
 C22-Cl23
 1.8 with sigma of 0.02
 Cl2-Cl3
 2.8 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C20 \\sim C22: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Cl2 \\sim Cl3 \\sim Cl23: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C20) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3)
\\sim Ueq, Uanis(Cl23) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Fixed Sof: Cl2(0.5) Cl3(0.5) Cl23(0.125) H20A(0.5) H20B(0.5) C22(0.5)
 H22A(0.5) H22B(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11),
 C13(H13), C15(H15)
5.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              58951
_olex2_submission_special_instructions 'No special instructions were received'