Heteroleptic Nickel Complexes for the Markovnikov-Selective Hydroboration of Styrenes
Touney, Eric E.; Van Hoveln, Ryan; Buttke, Carl T.; Freidberg, Michael D.; Guzei, Ilia A.; Schomaker, Jennifer M.; Organometallics 35 (2016) 3436–; doi:10.1021/acs.organomet.6b00652

data_4086748
_publ_section_title
;
 Heteroleptic Nickel Complexes for the Markovnikov-Selective Hydroboration
 of Styrenes
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              3436
_journal_paper_doi               10.1021/acs.organomet.6b00652
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety
'C45 H69 Cl2 N2 Ni P, 0.25(C12.47 H22.86 P0.69), 0.32(C7 H8)'
_chemical_formula_sum            'C50.31 H77.22 Cl2 N2 Ni P1.17'
_chemical_formula_weight         876.07
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-08-15
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.07.26 svn.r3321 for OlexSys, GUI svn.r5206)
;
_cell_angle_alpha                71.100(7)
_cell_angle_beta                 79.041(5)
_cell_angle_gamma                88.030(17)
_cell_formula_units_Z            8
_cell_length_a                   21.649(6)
_cell_length_b                   21.671(6)
_cell_length_c                   22.852(7)
_cell_measurement_reflns_used    9749
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.453
_cell_measurement_theta_min      2.272
_cell_volume                     9954(5)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX2 Ver. 2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            221546
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.576
_diffrn_reflns_theta_min         1.136
_exptl_absorpt_coefficient_mu    0.568
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6954
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3782
_exptl_crystal_size_max          0.174
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.137
_refine_diff_density_max         0.811
_refine_diff_density_min         -0.548
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2392
_refine_ls_number_reflns         41461
_refine_ls_number_restraints     1740
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0433P)^2^+9.4074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32980
_reflns_number_total             41461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00652_si_003.cif
_cod_data_source_block           schomaker52
_cod_depositor_comments
'Adding full bibliography for 4086747--4086749.cif.'
_cod_database_code               4086748
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.908
_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
C52C \\sim C53C \\sim C54C \\sim C55C \\sim C56C \\sim C57C \\sim C13C \\sim
C14C \\sim C15C \\sim C16C \\sim C17C \\sim C18C: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.01
C1C \\sim C2C \\sim C5C \\sim C46C \\sim C47C \\sim C50C \\sim C6C \\sim C51C
\\sim C3C \\sim C48C \\sim C4C \\sim C49C: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1B \\sim C2B \\sim C3B \\sim C6B \\sim C46B \\sim C47B \\sim C48B \\sim C51B
\\sim C4B \\sim C5B \\sim C49B \\sim C50B: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C30S \\sim C25S \\sim C26S \\sim C27S \\sim C31S \\sim C29S \\sim C8S \\sim P1S
\\sim C1S \\sim C7S \\sim C13S \\sim C19S \\sim C2S \\sim C6S \\sim C12S \\sim
C14S \\sim C18S \\sim C20S \\sim C24S \\sim C3S \\sim C5S \\sim C9S \\sim C11S
\\sim C15S \\sim C17S \\sim C21S \\sim C23S \\sim C4S \\sim C10S \\sim C16S
\\sim C22S \\sim C28S \\sim C38S \\sim C32S \\sim C33S \\sim C34S \\sim C35S
\\sim C37S \\sim C36S: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C42S \\sim C39S \\sim C40S \\sim C41S \\sim C45S \\sim C44S \\sim C43S \\sim
C48S \\sim C46S \\sim C47S \\sim C52S \\sim C49S \\sim C51S \\sim C50S: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{P1B, C1B, C2B, C3B, C4B, C5B, C6B} sigma for 1-2: 0.005, 1-3: 0.01
{P1B, C46B, C47B, C48B, C49B, C50B, C51B} sigma for 1-2: 0.005, 1-3: 0.01
{P1B, C13B, C14B, C15B, C16B, C17B, C18B} sigma for 1-2: 0.005, 1-3: 0.01
{P1C, C1C, C2C, C3C, C4C, C5C, C6C} sigma for 1-2: 0.005, 1-3: 0.01
{P1C, C13C, C14C, C15C, C16C, C17C, C18C} sigma for 1-2: 0.005, 1-3: 0.01
{P1C, C46C, C47C, C48C, C49C, C50C, C51C} sigma for 1-2: 0.005, 1-3: 0.01
{P1C, C52C, C53C, C54C, C55C, C56C, C57C} sigma for 1-2: 0.005, 1-3: 0.01
{P1S, C13S, C14S, C15S, C16S, C17S, C18S} sigma for 1-2: 0.005, 1-3: 0.01
{P1S, C19S, C20S, C21S, C22S, C23S, C24S} sigma for 1-2: 0.005, 1-3: 0.01
as
{P1, C1, C2, C3, C4, C5, C6}
4. Others
 -1*[Sof(P1S)+Sof(C1S)+Sof(H1S)+Sof(C2S)+Sof(H2SA)+Sof(H2SB)+Sof(C3S)+
 Sof(H3SA)+Sof(H3SB)+Sof(C4S)+Sof(H4SA)+Sof(H4SB)+Sof(C5S)+Sof(H5SA)+Sof(H5SB)+
 Sof(C6S)+Sof(H6SA)+Sof(H6SB)+Sof(C7S)+Sof(H7S)+Sof(C8S)+Sof(H8SA)+Sof(H8SB)+
 Sof(C9S)+Sof(H9SA)+Sof(H9SB)+Sof(C10S)+Sof(H10I)+Sof(H10J)+Sof(C11S)+Sof(H11I)+
 Sof(H11J)+Sof(C12S)+Sof(H12I)+Sof(H12J)]+1*[Sof(C13S)+Sof(H13S)+Sof(C14S)+
 Sof(H14I)+Sof(H14J)+Sof(C15S)+Sof(H15I)+Sof(H15J)+Sof(C16S)+Sof(H16I)+
 Sof(H16J)+Sof(C17S)+Sof(H17I)+Sof(H17J)+Sof(C18S)+Sof(H18I)+Sof(H18J)]+1*
 [Sof(C19S)+Sof(H19S)+Sof(C20S)+Sof(H20D)+Sof(H20E)+Sof(C21S)+Sof(H21D)+
 Sof(H21E)+Sof(C22S)+Sof(H22A)+Sof(H22B)+Sof(C23S)+Sof(H23A)+Sof(H23B)+
 Sof(C24S)+Sof(H24D)+Sof(H24E)]=0 with esd of 0
 Sof(C46B)=Sof(H46B)=Sof(C47B)=Sof(H47C)=Sof(H47D)=Sof(C48B)=Sof(H48C)=
 Sof(H48D)=Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(C50B)=Sof(H50C)=Sof(H50D)=
 Sof(C51B)=Sof(H51C)=Sof(H51D)=1-FVAR(1)
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C6B)=Sof(H6BA)=
 Sof(H6BB)=FVAR(1)
 Sof(C46C)=Sof(H46C)=Sof(C47C)=Sof(H47A)=Sof(H47B)=Sof(C48C)=Sof(H48A)=
 Sof(H48B)=Sof(C49C)=Sof(H49A)=Sof(H49B)=Sof(C50C)=Sof(H50A)=Sof(H50B)=
 Sof(C51C)=Sof(H51A)=Sof(H51B)=1-FVAR(2)
 Sof(C1C)=Sof(H1C)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(C3C)=Sof(H3CA)=Sof(H3CB)=
 Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(C5C)=Sof(H5CA)=Sof(H5CB)=Sof(C6C)=Sof(H6CA)=
 Sof(H6CB)=FVAR(2)
 Sof(C52C)=Sof(H52C)=Sof(C53C)=Sof(H53A)=Sof(H53B)=Sof(C54C)=Sof(H54A)=
 Sof(H54B)=Sof(C55C)=Sof(H55A)=Sof(H55B)=Sof(C56C)=Sof(H56A)=Sof(H56B)=
 Sof(C57C)=Sof(H57A)=Sof(H57B)=1-FVAR(3)
 Sof(C13C)=Sof(H13C)=Sof(C14C)=Sof(H14A)=Sof(H14B)=Sof(C15C)=Sof(H15A)=
 Sof(H15B)=Sof(C16C)=Sof(H16A)=Sof(H16B)=Sof(C17C)=Sof(H17A)=Sof(H17B)=
 Sof(C18C)=Sof(H18A)=Sof(H18B)=FVAR(3)
 Sof(P1S)=Sof(C1S)=Sof(H1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=Sof(H3SA)=
 Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(C6S)=
 Sof(H6SA)=Sof(H6SB)=Sof(C7S)=Sof(H7S)=Sof(C8S)=Sof(H8SA)=Sof(H8SB)=Sof(C9S)=
 Sof(H9SA)=Sof(H9SB)=Sof(C10S)=Sof(H10I)=Sof(H10J)=Sof(C11S)=Sof(H11I)=
 Sof(H11J)=Sof(C12S)=Sof(H12I)=Sof(H12J)=FVAR(4)
 Sof(C13S)=Sof(H13S)=Sof(C14S)=Sof(H14I)=Sof(H14J)=Sof(C15S)=Sof(H15I)=
 Sof(H15J)=Sof(C16S)=Sof(H16I)=Sof(H16J)=Sof(C17S)=Sof(H17I)=Sof(H17J)=
 Sof(C18S)=Sof(H18I)=Sof(H18J)=FVAR(5)
 Sof(C19S)=Sof(H19S)=Sof(C20S)=Sof(H20D)=Sof(H20E)=Sof(C21S)=Sof(H21D)=
 Sof(H21E)=Sof(C22S)=Sof(H22A)=Sof(H22B)=Sof(C23S)=Sof(H23A)=Sof(H23B)=
 Sof(C24S)=Sof(H24D)=Sof(H24E)=FVAR(6)
 Sof(C25S)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26S)=Sof(C27S)=Sof(H27S)=
 Sof(C28S)=Sof(H28S)=Sof(C29S)=Sof(H29S)=Sof(C30S)=Sof(H30S)=Sof(C31S)=
 Sof(H31S)=FVAR(7)
 Sof(C32S)=Sof(H32M)=Sof(H32N)=Sof(H32O)=Sof(C33S)=Sof(C34S)=Sof(H34S)=
 Sof(C35S)=Sof(H35S)=Sof(C36S)=Sof(H36S)=Sof(C37S)=Sof(H37S)=Sof(C38S)=
 Sof(H38S)=FVAR(8)
 Sof(C39S)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40S)=Sof(C41S)=Sof(H41S)=
 Sof(C42S)=Sof(H42S)=Sof(C43S)=Sof(H43S)=Sof(C44S)=Sof(H44S)=Sof(C45S)=
 Sof(H45S)=FVAR(9)
 Sof(C46S)=Sof(H46A)=Sof(H46D)=Sof(H46E)=Sof(C47S)=Sof(C48S)=Sof(H48S)=
 Sof(C49S)=Sof(H49S)=Sof(C50S)=Sof(H50S)=Sof(C51S)=Sof(H51S)=Sof(C52S)=
 Sof(H52S)=FVAR(10)
5.a Free rotating group:
 C25S(C26S,C27S,C28S,C29S,C30S,C31S), C32S(C33S,C34S,C35S,C36S,C37S,C38S),
 C39S(C40S,C41S,C42S,C43S,C44S,C45S), C46S(C47S,C48S,C49S,C50S,C51S,C52S)
5.b Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C28(H28), C31(H31), C40(H40), C43(H43), C1A(H1A),
 C7A(H7A), C13A(H13A), C28A(H28A), C31A(H31A), C40A(H40A), C43A(H43A),
 C13B(H13B), C1B(H1B), C46B(H46B), C7B(H7B), C28B(H28B), C31B(H31B), C40B(H40B),
  C43B(H43B), C52C(H52C), C1C(H1C), C46C(H46C), C7C(H7C), C13C(H13C),
 C28C(H28C), C31C(H31C), C40C(H40C), C43C(H43C), C19S(H19S), C1S(H1S), C7S(H7S),
  C13S(H13S)
5.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10E,H10F), C11(H11E,H11F), C12(H12E,H12F), C14(H14E,H14F),
 C15(H15E,H15F), C16(H16E,H16F), C17(H17E,H17F), C18(H18E,H18F), C2A(H2AA,H2AB),
  C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), C8A(H8AA,
 H8AB), C9A(H9AA,H9AB), C10A(H10G,H10H), C11A(H11G,H11H), C12A(H12G,H12H),
 C14A(H14G,H14H), C15A(H15G,H15H), C16A(H16G,H16H), C17A(H17G,H17H), C18A(H18G,
 H18H), C14B(H14C,H14D), C15B(H15C,H15D), C16B(H16C,H16D), C17B(H17C,H17D),
 C18B(H18C,H18D), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,
 H5BB), C6B(H6BA,H6BB), C47B(H47C,H47D), C48B(H48C,H48D), C49B(H49C,H49D),
 C50B(H50C,H50D), C51B(H51C,H51D), C8B(H8BA,H8BB), C9B(H9BA,H9BB), C10B(H10C,
 H10D), C11B(H11C,H11D), C12B(H12C,H12D), C53C(H53A,H53B), C54C(H54A,H54B),
 C55C(H55A,H55B), C56C(H56A,H56B), C57C(H57A,H57B), C2C(H2CA,H2CB), C3C(H3CA,
 H3CB), C4C(H4CA,H4CB), C5C(H5CA,H5CB), C6C(H6CA,H6CB), C47C(H47A,H47B),
 C48C(H48A,H48B), C49C(H49A,H49B), C50C(H50A,H50B), C51C(H51A,H51B), C8C(H8CA,
 H8CB), C9C(H9CA,H9CB), C10C(H10A,H10B), C11C(H11A,H11B), C12C(H12A,H12B),
 C14C(H14A,H14B), C15C(H15A,H15B), C16C(H16A,H16B), C17C(H17A,H17B), C18C(H18A,
 H18B), C20S(H20D,H20E), C21S(H21D,H21E), C22S(H22A,H22B), C23S(H23A,H23B),
 C24S(H24D,H24E), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,
 H5SB), C6S(H6SA,H6SB), C8S(H8SA,H8SB), C9S(H9SA,H9SB), C10S(H10I,H10J),
 C11S(H11I,H11J), C12S(H12I,H12J), C14S(H14I,H14J), C15S(H15I,H15J), C16S(H16I,
 H16J), C17S(H17I,H17J), C18S(H18I,H18J)
5.d Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C24(H24), C25(H25), C26(H26), C36(H36), C37(H37),
 C38(H38), C20A(H20A), C21A(H21A), C24A(H24A), C25A(H25A), C26A(H26A),
 C36A(H36A), C37A(H37A), C38A(H38A), C20B(H20B), C21B(H21B), C24B(H24B),
 C25B(H25B), C26B(H26B), C36B(H36B), C37B(H37B), C38B(H38B), C20C(H20C),
 C21C(H21C), C24C(H24C), C25C(H25C), C26C(H26C), C36C(H36C), C37C(H37C),
 C38C(H38C), C27S(H27S), C28S(H28S), C29S(H29S), C30S(H30S), C31S(H31S),
 C34S(H34S), C35S(H35S), C36S(H36S), C37S(H37S), C38S(H38S), C41S(H41S),
 C42S(H42S), C43S(H43S), C44S(H44S), C45S(H45S), C48S(H48S), C49S(H49S),
 C50S(H50S), C51S(H51S), C52S(H52S)
5.e Idealised Me refined as rotating group:
 C29(H29G,H29H,H29I), C30(H30G,H30H,H30I), C32(H32G,H32H,H32I), C33(H33G,H33H,
 H33I), C41(H41G,H41H,H41I), C42(H42G,H42H,H42I), C44(H44G,H44H,H44I), C45(H45G,
 H45H,H45I), C29A(H29J,H29K,H29L), C30A(H30J,H30K,H30L), C32A(H32J,H32K,H32L),
 C33A(H33J,H33K,H33L), C41A(H41J,H41K,H41L), C42A(H42J,H42K,H42L), C44A(H44J,
 H44K,H44L), C45A(H45J,H45K,H45L), C29B(H29D,H29E,H29F), C30B(H30D,H30E,H30F),
 C32B(H32D,H32E,H32F), C33B(H33D,H33E,H33F), C41B(H41D,H41E,H41F), C42B(H42D,
 H42E,H42F), C44B(H44D,H44E,H44F), C45B(H45D,H45E,H45F), C29C(H29A,H29B,H29C),
 C30C(H30A,H30B,H30C), C32C(H32A,H32B,H32C), C33C(H33A,H33B,H33C), C41C(H41A,
 H41B,H41C), C42C(H42A,H42B,H42C), C44C(H44A,H44B,H44C), C45C(H45A,H45B,H45C),
 C25S(H25D,H25E,H25F), C32S(H32M,H32N,H32O), C39S(H39A,H39B,H39C), C46S(H46A,
 H46D,H46E)
;
_shelx_res_checksum              55617
_shelx_hkl_checksum              33552
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-01-27
_olex2_date_sample_submission    2015-01-27
_olex2_submission_special_instructions 'No special instructions were received'