Deciphering the Mechanism of the Nickel-Catalyzed Hydroalkoxylation Reaction: A Combined Experimental and Computational Study
Mifleur, Alexis; Mérel, Delphine S.; Mortreux, André; Suisse, Isabelle; Capet, Frédéric; Trivelli, Xavier; Sauthier, Mathieu; Macgregor, Stuart A.; ACS Catalysis 7 (2017) 6915–; doi:10.1021/acscatal.7b00616

data_4514194
_publ_section_title
;
 Deciphering the Mechanism of the Nickel-Catalyzed Hydroalkoxylation
 Reaction: A Combined Experimental and Computational Study
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              6915
_journal_paper_doi               10.1021/acscatal.7b00616
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C36 H35 Cl Ni P2, C7 H8'
_chemical_formula_sum            'C43 H43 Cl Ni P2'
_chemical_formula_weight         715.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.19 svn.r3143 for OlexSys, GUI svn.r4992)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.111(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3832(5)
_cell_length_b                   17.1052(6)
_cell_length_c                   17.3844(7)
_cell_measurement_reflns_used    9195
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.05
_cell_measurement_theta_min      2.36
_cell_volume                     3537.7(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.0385
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            54710
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.094
_diffrn_reflns_theta_max         25.094
_diffrn_reflns_theta_min         1.704
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.745
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.1180 before and 0.0469 after correction. The Ratio of minimum to maximum transmission is 0.8961. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       plate
_exptl_crystal_F_000             1504
_exptl_crystal_size_max          0.385
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.131
_refine_diff_density_max         0.665
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     376
_refine_ls_number_reflns         6261
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0301
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0331P)^2^+2.6073P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0714
_refine_ls_wR_factor_ref         0.0747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5532
_reflns_number_total             6261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b00616_si_004.cif
_cod_data_source_block           mo_am451_0m_a_a_sq
_cod_depositor_comments
'Adding full bibliography for 4514194--4514195.cif.'
_cod_database_code               4514194
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.762
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C36A) = Uanis(C36)
Uanis(C35) = Uanis(C35A)
Uanis(C34) = Uanis(C34A)
Uanis(C33A) = Uanis(C33)
3. Others
 Sof(C34A)=Sof(H34A)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C35A)=Sof(H35A)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C34)=Sof(H34)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C35(H35), C34(H34), C34A(H34A), C35A(H35A)
4.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C13(H13A,H13B), C33(H33A,H33B), C33A(H33C,H33D)
4.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C17(H17), C18(H18), C23(H23), C2(H2), C32(H32), C3(H3), C15(H15),
 C16(H16), C6(H6), C26(H26), C31(H31), C28(H28), C24(H24), C25(H25), C5(H5),
 C29(H29), C8(H8), C12(H12), C4(H4), C10(H10), C30(H30), C9(H9), C11(H11)
4.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C36A(H36D,H36E,H36F)
;
_shelx_fab_checksum              59756
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'