Combined Experimental and Computational Studies of the Mechanism of Dehydrogenative Borylation of Terminal Alkynes Catalyzed by PNP Complexes of Iridium
Foley, Bryan J.; Bhuvanesh, Nattamai; Zhou, Jia; Ozerov, Oleg V.; ACS Catalysis  (2020) 9824–9836; doi:10.1021/acscatal.0c02455

data_4517967
_publ_section_title
;
 Combined Experimental and Computational Studies of the Mechanism of
 Dehydrogenative Borylation of Terminal Alkynes Catalyzed by PNP Complexes
 of Iridium
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              9824
_journal_page_last               9836
_journal_paper_doi               10.1021/acscatal.0c02455
_journal_year                    2020
_chemical_formula_moiety         '1(C36 H60 B2 Ir N O4 P2)'
_chemical_formula_sum            'C36 H60 B2 Ir N O4 P2'
_chemical_formula_weight         846.61
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-12
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                84.689(3)
_cell_angle_beta                 89.852(3)
_cell_angle_gamma                71.719(3)
_cell_formula_units_Z            4
_cell_length_a                   14.485(3)
_cell_length_b                   16.260(4)
_cell_length_c                   17.548(4)
_cell_measurement_reflns_used    6157
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.570
_cell_measurement_theta_min      2.481
_cell_volume                     3906.0(15)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.0
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.973
_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  0.0483
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            17596
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.580
_diffrn_reflns_theta_min         1.647
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.536
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0726 before and 0.0508 after correction.
 The Ratio of minimum to maximum transmission is 0.77.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 53760 reflections, Rint = 0.0483
 (23978 with I > 3sig(I), Rint = 0.0390)
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       block
_exptl_crystal_F_000             1728
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.029
_refine_diff_density_max         3.696
_refine_diff_density_min         -1.943
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1161
_refine_ls_number_reflns         17596
_refine_ls_number_restraints     1864
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0724
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0572P)^2^+3.0208P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13005
_reflns_number_total             17596
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02455_si_003.cif
_cod_data_source_block           bjf189
_cod_depositor_comments          'Adding full bibliography for 4517967.cif.'
_cod_original_cell_volume        3906.2(15)
_cod_database_code               4517967
_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. Restrained distances
 C25-C26 = C25-C27 = C28-C29 = C28-C30 = C31-C32 = C31-C33 = C34-C35 = C34-C36
 = C25B-C26B = C25B-C27B = C28B-C29B = C28B-C30B = C31B-C32B = C31B-C33B = C34B-
 C35B = C34B-C36B
 1.54 with sigma of 0.02
 C29-C30 = C26-C27 = C32-C33 = C35-C36 = C26B-C27B = C29B-C30B = C32B-C33B =
 C35B-C36B
 2.54 with sigma of 0.02
 Ir1-B1 \\sim Ir1-B1A \\sim Ir1-B2 \\sim Ir1-B2A \\sim Ir1B-B1C \\sim Ir1B-B1B
\\sim Ir1B-B2C \\sim Ir1B-B2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
B1 \\sim O1 \\sim O2 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim
C30 \\sim B1A \\sim O1A \\sim O2A \\sim C25A \\sim C26A \\sim C27A \\sim C28A
\\sim C29A \\sim C30A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
B2 \\sim O3 \\sim O4 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim
C36 \\sim B2A \\sim O3A \\sim O4A \\sim C31A \\sim C32A \\sim C33A \\sim C34A
\\sim C35A \\sim C36A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
B1B \\sim O1B \\sim O2B \\sim C25B \\sim C26B \\sim C27B \\sim C28B \\sim C29B
\\sim C30B \\sim B1C \\sim O1C \\sim O2C \\sim C25C \\sim C27C \\sim C28C \\sim
C29C \\sim C30C \\sim C26C: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
B2B \\sim O3B \\sim O4B \\sim C31B \\sim C32B \\sim C33B \\sim C34B \\sim C35B
\\sim C36B \\sim B2C \\sim O3C \\sim O4C \\sim C31C \\sim C32C \\sim C33C \\sim
C34C \\sim C35C \\sim C36C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(B1) = Uanis(B1A)
Uanis(B2) = Uanis(B2A)
Uanis(B1B) = Uanis(B1C)
Uanis(C30B) = Uanis(C30C)
Uanis(C26B) = Uanis(C28C)
Uanis(B2B) = Uanis(B2C)
4. Rigid body (RIGU) restrains
 B1, O1, O2, C25, C26, C27, C28, C29, C30, B1A, O1A, O2A, C25A, C26A, C27A,
 C28A, C29A, C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B2, O3, O4, C31, C32, C33, C34, C35, C36, B2A, O3A, O4A, C31A, C32A, C33A,
 C34A, C35A, C36A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B1B, O1B, O2B, C25B, C26B, C27B, C28B, C29B, C30B, B1C, O1C, O2C, C25C, C27C,
 C28C, C29C, C30C, C26C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B2B, O3B, O4B, C31B, C32B, C33B, C34B, C35B, C36B, B2C, O3C, O4C, C31C, C32C,
 C33C, C34C, C35C, C36C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Same fragment restrains
{B1, O1, O2, C25, C26, C27, C28, C29, C30} sigma for 1-2: 0.005, 1-3: 0.04
as
{B1A, O1A, O2A, C25A, C26A, C27A, C28A, C29A, C30A}
{B2, O3, O4, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.005, 1-3: 0.04
as
{B2A, O3A, O4A, C31A, C32A, C33A, C34A, C35A, C36A}
{B1B, O1B, O2B, C25B, C26B, C27B, C28B, C29B, C30B} sigma for 1-2: 0.005, 1-3:
0.04
as
{B1C, O1C, O2C, C25C, C27C, C28C, C29C, C30C, C26C}
{B2B, O3B, O4B, C31B, C32B, C33B, C34B, C35B, C36B} sigma for 1-2: 0.005, 1-3:
0.04
as
{B2C, O3C, O4C, C31C, C32C, C33C, C34C, C35C, C36C}
6. Others
 Sof(B1A)=Sof(O1A)=Sof(O2A)=Sof(C25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(B2A)=Sof(O3A)=
 Sof(O4A)=Sof(C31A)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(B1C)=Sof(O1C)=Sof(O2C)=Sof(C25C)=
 Sof(C27C)=Sof(H27J)=Sof(H27K)=Sof(H27L)=Sof(C28C)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C29C)=Sof(C30C)=Sof(H30J)=Sof(H30K)=Sof(H30L)=Sof(C26C)=
 Sof(H26J)=Sof(H26K)=Sof(H26L)=Sof(B2C)=Sof(O3C)=Sof(O4C)=Sof(C31C)=Sof(C32C)=
 Sof(H32J)=Sof(H32K)=Sof(H32L)=Sof(C33C)=Sof(H33J)=Sof(H33K)=Sof(H33L)=
 Sof(C34C)=Sof(C35C)=Sof(H35J)=Sof(H35K)=Sof(H35L)=Sof(C36C)=Sof(H36J)=
 Sof(H36K)=Sof(H36L)=1-FVAR(1)
 Sof(B1)=Sof(O1)=Sof(O2)=Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(B2)=Sof(O3)=Sof(O4)=
 Sof(C31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(B1B)=Sof(O1B)=Sof(O2B)=Sof(C25B)=Sof(C26B)=Sof(H26G)=
 Sof(H26H)=Sof(H26I)=Sof(C27B)=Sof(H27G)=Sof(H27H)=Sof(H27I)=Sof(C28B)=
 Sof(C29B)=Sof(H29G)=Sof(H29H)=Sof(H29I)=Sof(C30B)=Sof(H30G)=Sof(H30H)=
 Sof(H30I)=Sof(B2B)=Sof(O3B)=Sof(O4B)=Sof(C31B)=Sof(C32B)=Sof(H32G)=Sof(H32H)=
 Sof(H32I)=Sof(C33B)=Sof(H33G)=Sof(H33H)=Sof(H33I)=Sof(C34B)=Sof(C35B)=
 Sof(H35G)=Sof(H35H)=Sof(H35I)=Sof(C36B)=Sof(H36G)=Sof(H36H)=Sof(H36I)=FVAR(1)
7.a Riding coordinates:
 C19(H19A,H19B,H19C), C27A(H27D,H27E,H27F), C35(H35A,H35B,H35C), C16B(H16D,
 H16E,H16F), C35C(H35J,H35K,H35L)
7.b Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C15B(H15B), C18B(H18B)
7.c Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C23(H23A,H23B), C21B(H21C,H21D), C23B(H23C,H23D)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C3B(H3B), C5B(H5B),
 C6B(H6B), C9B(H9B), C10B(H10B), C12B(H12B)
7.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C26A(H26D,H26E,H26F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C36(H36A,H36B,H36C), C32A(H32D,H32E,H32F),
 C33A(H33D,H33E,H33F), C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F), C7B(H7BA,
 H7BB,H7BC), C14B(H14D,H14E,H14F), C17B(H17D,H17E,H17F), C19B(H19D,H19E,H19F),
 C20B(H20D,H20E,H20F), C22B(H22D,H22E,H22F), C24B(H24D,H24E,H24F), C26B(H26G,
 H26H,H26I), C27B(H27G,H27H,H27I), C29B(H29G,H29H,H29I), C30B(H30G,H30H,H30I),
 C27C(H27J,H27K,H27L), C28C(H28A,H28B,H28C), C30C(H30J,H30K,H30L), C26C(H26J,
 H26K,H26L), C32B(H32G,H32H,H32I), C33B(H33G,H33H,H33I), C35B(H35G,H35H,H35I),
 C36B(H36G,H36H,H36I), C32C(H32J,H32K,H32L), C33C(H33J,H33K,H33L), C36C(H36J,
 H36K,H36L)
;
_shelx_res_checksum              16750
_shelx_hkl_checksum              57803
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'