Role of High-Spin Species and Pendant Amines in Electrocatalytic Alcohol Oxidation by a Nickel Phosphine Complex
Gunasekara, Thilina; Tong, Yicheng; Speelman, Amy L.; Erickson, Jeremy D.; Appel, Aaron M.; Hall, Michael B.; Wiedner, Eric S.; ACS Catalysis  (2022) 2729–2740; doi:10.1021/acscatal.1c05509

data_4519335
_publ_section_title
;
 Role of High-Spin Species and Pendant Amines in Electrocatalytic Alcohol
 Oxidation by a Nickel Phosphine Complex
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2729
_journal_page_last               2740
_journal_paper_doi               10.1021/acscatal.1c05509
_journal_year                    2022
_chemical_formula_moiety
'0.75(C31 H56 N2 Ni P2), 0.25(C31 H55 N2 Ni P2), 2(B F4), 0.5(C2 H3 N)'
_chemical_formula_sum            'C32 H57.25 B2 F8 N2.5 Ni P2'
_chemical_formula_weight         771.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-11-18
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_cell_angle_alpha                106.291(4)
_cell_angle_beta                 97.137(3)
_cell_angle_gamma                92.346(3)
_cell_formula_units_Z            8
_cell_length_a                   12.1730(11)
_cell_length_b                   20.1578(16)
_cell_length_c                   33.802(3)
_cell_measurement_reflns_used    9900
_cell_measurement_temperature    107(2)
_cell_measurement_theta_max      26.497
_cell_measurement_theta_min      2.253
_cell_volume                     7874.6(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      107.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0572
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            420364
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         1.869
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.637
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6356
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1460 before and 0.0800 after correction. The Ratio of minimum to maximum transmission is 0.8527. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             3254
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.395
_exptl_crystal_size_min          0.352
_refine_diff_density_max         2.015
_refine_diff_density_min         -0.982
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.209
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1742
_refine_ls_number_reflns         31000
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.210
_refine_ls_R_factor_all          0.1183
_refine_ls_R_factor_gt           0.1166
_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^)+123.3470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2648
_refine_ls_wR_factor_ref         0.2654
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29998
_reflns_number_total             31000
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05509_si_002.cif
_cod_data_source_block           jdeals05f_a
_cod_original_formula_sum        'C32 H57.25 B2 F8 N2.50 Ni P2'
_cod_database_code               4519335
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.807
_shelx_estimated_absorpt_t_min   0.785
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C021-C04I \\sim C021-C0AA
 with sigma of 0.02
 C04I-C04L \\sim C0AA-C04L
 with sigma of 0.02
 C036-C052 \\sim C036-C0
 with sigma of 0.02
 C03S-C052 \\sim C03S-C0
 with sigma of 0.02
 F04D-B04R \\sim F04E-B04R
 with sigma of 0.02
 F04Q-B04R \\sim F04R-B04R
 with sigma of 0.02
 B04R-F04U \\sim B04R-F04V
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(H02T)=Sof(H02U)=1-FVAR(1)
 Sof(H02R)=Sof(H02S)=FVAR(1)
 Fixed Sof: H03F(0.66667) H03G(0.66667) H03H(0.33333) H03I(0.33333)
 H03T(0.66667) H03U(0.66667) H03V(0.33333) H03W(0.33333) F04D(0.66667)
 H04G(0.5) C04I(0.75) H04K(0.75) H04L(0.75) H04O(0.75) H04P(0.75) H04Q(0.25)
 H04R(0.25) H04S(0.5) F04Q(0.66667) F04U(0.66667) C052(0.66667) H05A(0.66667)
 H05B(0.66667) C0AA(0.25) H0AA(0.25) H0AB(0.25) C0(0.33333) H0A(0.33333)
 H0B(0.33333) F04R(0.33333) F04V(0.33333) F04E(0.33333)
5.a Ternary CH refined with riding coordinates:
 C017(H017), C01F(H01G), C01H(H01J), C01M(H01), C01N(H01N), C01P(H30),
 C01S(H01S), C01X(H01X), C01Z(H01Z), C026(H026), C02A(H13), C02D(H34),
 C02F(H35), C02I(H02I), C02M(H02Z), C03L(H6)
5.b Secondary CH2 refined with riding coordinates:
 C019(H01A,H01B), C01D(H01H,H01I), C01I(H01V,H01W), C01J(H01C,H01D), C01K(H01Y,
 H), C01L(H01K,H01L), C01O(H01M,H01O), C01U(H31,HA), C01V(H01E,H01F), C01W(H01T,
 H01U), C020(H10,HB), C021(H02R,H02S), C021(H02T,H02U), C022(H02A,H02B),
 C023(H02C,H02D), C024(H11,HC), C025(H02V,H02W), C028(H12,HD), C029(H32,HE),
 C02B(H33,HF), C02C(H14,HG), C02E(H02X,H02Y), C02G(H15,HH), C02H(H02E,H02F),
 C02J(H02G,H02H), C02K(H36,HI), C02L(H02J,H02K), C02N(H37,HJ), C02O(H16,HK),
 C02P(H38,HL), C02Q(H39,HM), C02R(H02,HN), C02S(H02L,H02M), C02T(H40,HO),
 C02U(H1,HP), C02V(H41,HQ), C02W(H02N,H02O), C02X(H42,HR), C02Y(H02P,H02Q),
 C02Z(H2,HS), C030(H43,HT), C033(H03D,H03E), C034(H44,HU), C036(H03F,H03G),
 C036(H03H,H03I), C037(H03,HX), C038(H03J,H03K), C03A(H45,HY), C03C(H3,H57),
 C03D(H18,H58), C03E(H4,H59), C03F(H46,H60), C03G(H03L,H03M), C03H(H47,H61),
 C03I(H5,H62), C03J(H48,H63), C03K(H19,H64), C03M(H20,H65), C03N(H03N,H03O),
 C03O(H49,H66), C03P(H03P,H03Q), C03Q(H03R,H03S), C03R(H7,H67), C03S(H03T,H03U),
  C03S(H03V,H03W), C03T(H50,H68), C03U(H8,H69), C03V(H51,H70), C03W(H21,H71),
 C03X(H9,H72), C03Y(H03X,H03Y), C03Z(H22,H73), C040(H04,H74), C041(H04E,H04F),
 C042(H04A,H04B), C043(H52,H75), C046(H23,H76), C047(H24,H77), C048(H25,H78),
 C049(H26,H79), C04A(H27,H80), C04B(H28,H81), C04C(H29,H82), C04E(H04G,H04H),
 C04F(H04I,H04J), C04G(H53,H83), C04I(H04K,H04L), C04J(H04M,H04N), C04L(H04O,
 H04P), C04L(H04Q,H04R), C04M(H04S,H04T), C04N(H04U,H04V), C04O(H04C,H04D),
 C04P(H04W,H04X), C04X(H04Z,H88), C052(H05A,H05B), C0AA(H0AA,H0AB), C0(H0A,H0B)
5.c Idealised Me refined as rotating group:
 C01Q(H01P,H01Q,H01R), C031(H03A,H03B,H03C), C035(H03Z,HV,HW), C03B(H17,HZ,
 H56), C04S(H54,H84,H85), C04T(H04Y,H86,H87), C04Y(H55,H89,H90), C055(H05C,H05D,
 H05E), C05D(H05F,H05G,H05H), C05G(H05I,H05J,H05K)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 122 electrons were 
found in a volume of 474\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.313[C2H3N], 0.375[C2H3N] per Asymmetric Unit 
which account for 121 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2