Structural, Spectroscopic, and Kinetic Investigation of the Molybdenum Dialkylhydrazido Complexes [MoBr(NNC5H10)(dppe)2]Br and [Mo(NNC5H10)(dppe)2]: Activation Parameters and Revised Mechanism for N-N Cleavage
Ameli Dreher; Klaus Mersmann; Christian Näther; Ivana Ivanovic-Burmazovic; Rudi van Eldik; Felix Tuczek; Inorganic Chemistry 48 (2009) 2078–2093; doi:10.1021/ic801952v

data_4301573
_publ_section_title
;
Structural, Spectroscopic, and Kinetic Investigation of the Molybdenum
Dialkylhydrazido Complexes [MoBr(NNC5H10)(dppe)2]Br and
[Mo(NNC5H10)(dppe)2]: Activation Parameters and Revised Mechanism for N-N
Cleavage
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              2078
_journal_page_last               2093
_journal_paper_doi               10.1021/ic801952v
_journal_volume                  48
_journal_year                    2009
_chemical_formula_sum            'C57 H58 Mo N2 P4'
_chemical_formula_weight         990.87
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 108.954(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.3478(13)
_cell_length_b                   19.9745(16)
_cell_length_c                   16.6728(13)
_cell_measurement_reflns_used    8000
_cell_measurement_temperature    220(2)
_cell_measurement_theta_max      25
_cell_measurement_theta_min      11
_cell_volume                     5149.1(8)
_computing_cell_refinement       'STOE IPDS-1 program package'
_computing_data_collection       'STOE IPDS-1 program package'
_computing_data_reduction        'STOE IPDS-1 program package'
_computing_molecular_graphics    'XP in SHELXTL-PC'
_computing_publication_material  'XCIF in SHELXTL-PC'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      220(2)
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'STOE IPDS-1'
_diffrn_measurement_method       Phi-scans
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_av_sigmaI/netI    0.0347
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            21991
_diffrn_reflns_theta_full        26.88
_diffrn_reflns_theta_max         26.88
_diffrn_reflns_theta_min         2.36
_diffrn_standards_decay_%        0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.417
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2064
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.698
_refine_diff_density_rms         0.062
_refine_ls_extinction_coef       0.0023(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         5504
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0327
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0575P)^2^+1.1851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0836
_refine_ls_wR_factor_ref         0.0863
_reflns_number_gt                4792
_reflns_number_total             5504
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic801952v_si_001.cif
_cod_data_source_block           felix39
_cod_original_cell_volume        5149.1(7)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4301573