Solvent Effects and Activation Parameters in the Competitive Cleavage of C-CN and C-H Bonds in 2-Methyl-3-Butenenitrile Using [(dippe)NiH]2
Brett D. Swartz; Nicole M. Reinartz; William W. Brennessel; Juventino J. García; William D. Jones; Journal of the American Chemical Society 130 (2008) 8548–8554; doi:10.1021/ja8000216

data_4107938
_publ_contact_author_address
'Department of Chemistry, University of Rochester, Rochester, New York 14627'
_publ_contact_author_email       jones@chem.rochester.edu
_publ_contact_author_name        'William D. Jones'
_publ_section_title
;
 Solvent Effects and Activation Parameters in the Competitive Cleavage of
 C-CN and C-H Bonds in 2-Methyl-3-Butenenitrile Using [(dippe)NiH]2
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8548
_journal_page_last               8554
_journal_paper_doi               10.1021/ja8000216
_journal_volume                  130
_journal_year                    2008
_chemical_formula_moiety         'C19 H38 N Ni P2, C24 H20 B'
_chemical_formula_sum            'C43 H58 B N Ni P2'
_chemical_formula_weight         720.36
_chemical_name_common            jonbds05
_chemical_name_systematic
;
 10,  [Ni(dippe)(2-cyanobutenyl)]+ BPh4-
;
_space_group_IT_number           43
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'F 2 -2d'
_symmetry_space_group_name_H-M   'F d d 2'
_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            16
_cell_length_a                   17.418(4)
_cell_length_b                   62.197(14)
_cell_length_c                   14.634(3)
_cell_measurement_reflns_used    4054
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      24.29
_cell_measurement_theta_min      2.43
_cell_volume                     15854(6)
_computing_cell_refinement       'SAINT (Bruker, 2006)'
_computing_data_collection       'APEX2 (Bruker, 2006)'
_computing_data_reduction        'SAINT (Bruker, 2006)'
_computing_molecular_graphics    'SHELXTL (Bruker, 2000)'
_computing_publication_material  'SHELXTL (Bruker, 2000)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR97 (Altomare et al., 1999)'
_diffrn_ambient_temperature      100.0(1)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART APEX II CCD Platform'
_diffrn_measurement_method       'area detector, \w scans per \f'
_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  0.1762
_diffrn_reflns_av_sigmaI/netI    0.1383
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       82
_diffrn_reflns_limit_k_min       -82
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            53976
_diffrn_reflns_theta_full        28.28
_diffrn_reflns_theta_max         28.28
_diffrn_reflns_theta_min         1.85
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_T_max  0.9940
_exptl_absorpt_correction_T_min  0.9154
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Blessing, 1995)'
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_description       needle
_exptl_crystal_F_000             6176
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.475
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
'Flack H D (1983), 4699 Friedel pairs, Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.014(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         9806
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.1465
_refine_ls_R_factor_gt           0.0678
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0258P)^2^+24.0423P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1067
_refine_ls_wR_factor_ref         0.1299
_reflns_number_gt                5447
_reflns_number_total             9806
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8000216-file005.cif
_cod_data_source_block           jonbds05
_cod_original_cell_volume        15853(6)
_cod_database_code               4107938