Normal and Inverse Primary Kinetic Deuterium Isotope Effects for C-H Bond Reductive Elimination and Oxidative Addition Reactions of Molybdenocene and Tungstenocene Complexes: Evidence for Benzene σ-Complex Intermediates
David G. Churchill; Kevin E. Janak; Joshua S. Wittenberg; Gerard Parkin; Journal of the American Chemical Society 125 (2003) 1403–1420; doi:10.1021/ja027670k

data_4113426
_publ_section_title
;
 Normal and Inverse Primary Kinetic Deuterium Isotope Effects for C-H Bond
 Reductive Elimination and Oxidative Addition Reactions of Molybdenocene
 and Tungstenocene Complexes: Evidence for Benzene \s-Complex
 Intermediates
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1403
_journal_page_last               1420
_journal_paper_doi               10.1021/ja027670k
_journal_volume                  125
_journal_year                    2003
_chemical_formula_sum            'C21 H34 Si W'
_chemical_formula_weight         498.42
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           62
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_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                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.257(3)
_cell_length_b                   14.744(6)
_cell_length_c                   13.261(5)
_cell_measurement_temperature    243(2)
_cell_volume                     2005.5(13)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      243(2)
_diffrn_measured_fraction_theta_full 0.952
_diffrn_measured_fraction_theta_max 0.952
_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  0.1108
_diffrn_reflns_av_sigmaI/netI    0.1140
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13447
_diffrn_reflns_theta_full        28.36
_diffrn_reflns_theta_max         28.36
_diffrn_reflns_theta_min         2.07
_exptl_absorpt_coefficient_mu    5.818
_exptl_absorpt_correction_T_max  0.5938
_exptl_absorpt_correction_T_min  0.3891
_exptl_crystal_density_diffrn    1.651
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         1.134
_refine_diff_density_min         -2.488
_refine_diff_density_rms         0.201
_refine_ls_extinction_coef       0.00076(17)
_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   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     116
_refine_ls_number_reflns         2474
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1317
_refine_ls_R_factor_gt           0.0527
_refine_ls_shift/su_max          0.083
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0506P)^2^+5.5834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1266
_reflns_number_gt                1379
_reflns_number_total             2474
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja027670k-5_s1_2.cif
_cod_data_source_block           ds10
_cod_original_cell_volume        2005.6(13)
_cod_database_code               4113426