Reversible Addition of Ethylene to a Pincer-Based Boryl-Iridium Unit with the Formation of a Bridging Ethylidene
Cao, Yihan; Shih, Wei-Chun; Bhuvanesh, Nattamai; Ozerov, Oleg V.; Chemical Science  (2020) –; doi:10.1039/D0SC04748A

data_1559270
_publ_section_title
;
 Reversible Addition of Ethylene to a Pincer-Based Boryl-Iridium Unit with
 the Formation of a Bridging Ethylidene
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04748A
_journal_year                    2020
_chemical_formula_moiety         'C27 H39.07 B Ir O P2, C27 H38.7 B Ir O P2'
_chemical_formula_sum            'C54 H77.78 B2 Ir2 O2 P4'
_chemical_formula_weight         1288.83
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-06
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2018-07-27 deposited with the CCDC.	2020-10-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.4602(7)
_cell_length_b                   18.1913(8)
_cell_length_c                   16.0356(6)
_cell_measurement_reflns_used    9806
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.381
_cell_measurement_theta_min      2.497
_cell_volume                     5385.0(4)
_computing_cell_refinement       'SAINT V8.38A (2016)'
_computing_data_reduction        'SAINT V8.38A (2016)'
_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 0.999
_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  0.0575
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            59403
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         1.572
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.095
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5112
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1181 before and 0.0515 after correction. The Ratio of minimum to maximum transmission is 0.6856. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.590
_exptl_crystal_description       block
_exptl_crystal_F_000             2567
_exptl_crystal_size_max          0.395
_exptl_crystal_size_mid          0.299
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.165
_refine_diff_density_min         -1.158
_refine_diff_density_rms         0.116
_refine_ls_abs_structure_details
;
 Flack x determined using 3846 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     641
_refine_ls_number_reflns         9428
_refine_ls_number_restraints     421
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0339
_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^)+23.9640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0651
_refine_ls_wR_factor_ref         0.0670
_reflns_Friedel_coverage         0.918
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                8748
_reflns_number_total             9428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04748a2.cif
_cod_data_source_block           yhc22xa
_cod_database_code               1559270
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.544(10)
 0.456(10)
2. 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
3. Restrained distances
 O2-C52 \\sim O2A-C52A
 with sigma of 0.01
 P4-C49 \\sim P4A-C49A
 with sigma of 0.01
 C50-C49 \\sim C50A-C49A \\sim C51A-C49A \\sim C51-C49
 with sigma of 0.01
 Ir1A-C26A \\sim Ir2-C53
 with sigma of 0.01
 Ir2A-P3 \\sim Ir2-P3 \\sim Ir2A-P4A \\sim Ir2-P4 \\sim Ir1A-P1 \\sim Ir1-P1
\\sim Ir1-P2 \\sim Ir1A-P2
 with sigma of 0.01
 C27A-C26A \\sim C54-C53
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Ir2 \\sim C34 \\sim B2: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Ir1 \\sim P2 \\sim O1 \\sim C11 \\sim C12 \\sim C25: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
C32 \\sim C33: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C26 \\sim C27 \\sim B1: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C31 \\sim C32 \\sim C33 \\sim B2: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Ir2 \\sim C52 \\sim O2 \\sim Ir2A \\sim C52A \\sim O2A \\sim C53 \\sim C54
\\sim C54A \\sim P4 \\sim P4A \\sim C49 \\sim C50 \\sim C51 \\sim C49A \\sim
C50A \\sim C51A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C26) = Uanis(C27)
Uanis(C52A) = Uanis(C52)
Uanis(O2) = Uanis(O2A)
Uanis(Ir2) = Uanis(Ir2A)
Uanis(C54) = Uanis(C54A)
Uanis(Ir1) = Uanis(Ir1A)
Uanis(C26) = Uanis(C26A)
Uanis(C27A) = Uanis(C27)
Uanis(P4) = Uanis(P4A)
5. Rigid body (RIGU) restrains
 Ir2, C34, B2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 Ir1, P2, O1, C11, C12, C25
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C32, C33
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C26, C27, B1
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.0005
 C31, C32, C33, B2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 Ir2, C52, O2, Ir2A, C52A, O2A, C53, C54, C54A, P4, P4A, C49, C50, C51, C49A,
 C50A, C51A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Others
 Sof(H53A)=Sof(Ir2A)=Sof(P4A)=Sof(C52A)=Sof(O2A)=Sof(C54A)=Sof(H54D)=Sof(H54E)=
 Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(C51A)=
 Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(1)
 Sof(Ir2)=Sof(P4)=Sof(C52)=Sof(O2)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(H51C)=Sof(H53)=FVAR(1)
 Sof(Ir1A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(H27E)=1-FVAR(2)
 Sof(Ir1)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=FVAR(2)
7.a Riding coordinates:
 C51(H51A,H51B,H51C), C51A(H51D,H51E,H51F), C27A(H27C,H27D,H27E)
7.b Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C22(H22), C26(H26), C49(H49), C40(H40),
 C43(H43), C53(H53), C53(H53A), C49A(H49A), C26A(H26A)
7.c Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C54A(H54D,H54E)
7.d Me refined with riding coordinates:
 C54(H54A,H54B,H54C)
7.e Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C29(H29),
 C30(H30), C31(H31), C32(H32), C35(H35), C36(H36), C37(H37), C38(H38)
7.f Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C50(H50A,H50B,H50C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C50A(H50D,H50E,H50F)
;
_shelx_res_checksum              31093
_olex2_submission_special_instructions 'No special instructions were received'