Bimetallic N-Heterocyclic Carbene Rh(I) Complexes: Probing the Cooperative Effect for the Catalyzed Hydroelementation of Alkynes
Diachenko, Vera; Page, Michael J.; Gatus, Mark R. D.; Bhadbhade, Mohan; Messerle, Barbara A.; Organometallics 34 (2015) 4543–; doi:10.1021/acs.organomet.5b00594

data_4086243
_publ_section_title
;
 Bimetallic N-Heterocyclic Carbene Rh(I) Complexes: Probing the
 Cooperative Effect for the Catalyzed Hydroelementation of Alkynes
;
_journal_issue                   18
_journal_name_full               Organometallics
_journal_page_first              4543
_journal_paper_doi               10.1021/acs.organomet.5b00594
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C38 H46 N8 Rh2, 3(C3 H6 O), 2(C24 H20 B)'
_chemical_formula_sum            'C95 H104 B2 N8 O3 Rh2'
_chemical_formula_weight         1633.30
_chemical_name_systematic
;
 ?
;
_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
_audit_creation_date             2014-11-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.20 svn.r3092 for OlexSys, GUI svn.r4949)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.2960(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6135(11)
_cell_length_b                   11.1826(6)
_cell_length_c                   43.152(3)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.431
_cell_measurement_theta_min      2.201
_cell_volume                     8927.8(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.01
_diffrn_measured_fraction_theta_max 0.995
_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  0.0677
_diffrn_reflns_av_unetI/netI     0.0910
_diffrn_reflns_laue_measured_fraction_full 0.892
_diffrn_reflns_laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            76601
_diffrn_reflns_point_group_measured_fraction_full 0.892
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.300
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.421
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0987 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.8817.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.215
_exptl_crystal_description       plate
_exptl_crystal_F_000             3416
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.068
_refine_diff_density_max         3.283
_refine_diff_density_min         -2.729
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.879
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1094
_refine_ls_number_reflns         15650
_refine_ls_number_restraints     184
_refine_ls_restrained_S_all      0.879
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0745
_refine_ls_shift/su_max          0.039
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1134P)^2^+53.6828P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1899
_refine_ls_wR_factor_ref         0.2085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11177
_reflns_number_total             15650
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00594_si_002.cif
_cod_data_source_block           vera_08oct13_a
_cod_original_cell_volume        8927.9(9)
_cod_database_code               4086243
_shelxl_version_number           2014-3
_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. Shared sites
{C1SA, C1SB}
3. Restrained distances
 C6DA-C5DA = C6DB-C5DB = C2DA-C1DA = C2DB-C1DB
 1.36 with sigma of 0.02
 C8DB-C1DB = C8DA-C1DA = C8DB-C7DB = C8DA-C7DA = C7DA-C6DA = C7DB-C6DB
 1.54 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(C1SA) = Uanis(C1SB)
5. Rigid body (RIGU) restrains
 C21E, C24E, C25E, C26E, B1E
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C21E, C24E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21E, C22E, C23E, C24E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1SA, C2SA, C3SA, C4SA, C5SA, C6SA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1SA, C2SB, C3SB, C4SB, C5SB, C6SB
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1TA, C6TA, C5TA, C4TA, C3TA, C2TA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1TB, C6TB, C5TB, C4TB, C3TB, C2TB
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2DC, C3DC, C1DC
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C1DA(0.75) H1DA(0.75) C7DA(0.75) H7DA(0.75) H7DB(0.75) C3DA(0.75)
 H3DA(0.75) H3DB(0.75) C4DA(0.75) H4DA(0.75) H4DB(0.75) C1DB(0.25) H1DB(0.25)
 C5DB(0.25) H5DB(0.25) C8DB(0.25) H8DA(0.25) H8DB(0.25) C2DB(0.25) H2DB(0.25)
 C6DB(0.25) H6DB(0.25) C3DB(0.25) H3DC(0.25) H3DD(0.25) C4DB(0.25) H4DC(0.25)
 H4DD(0.25) C7DB(0.25) H7DC(0.25) H7DD(0.25) C5DA(0.75) H5DA(0.75) C2DA(0.75)
 H2DA(0.75) C8DA(0.75) H8DC(0.75) H8DD(0.75) C6DA(0.75) H6DA(0.75) O1DC(0.5)
 C2DC(0.5) C3DC(0.5) H3DE(0.5) H3DF(0.5) H3DG(0.5) C1DC(0.5) H1DC(0.5)
 H1DD(0.5) H1DE(0.5) O1BC(0.5) C3BC(0.5) H3BA(0.5) H3BB(0.5) H3BC(0.5)
 C1BC(0.5) H1BA(0.5) H1BB(0.5) H1BC(0.5) C2BC(0.5) C3SA(0.6) H3SA(0.6)
 C5SA(0.6) H5SA(0.6) C2SA(0.6) H2SA(0.6) C4SA(0.6) H4SA(0.6) C1SA(0.6)
 C2SB(0.4) H2SB(0.4) C3SB(0.4) H3SB(0.4) C4SB(0.4) H4SB(0.4) C5SB(0.4)
 H5SB(0.4) C6SB(0.4) H6SB(0.4) C1TB(0.5) C6TB(0.5) H6TB(0.5) C5TB(0.5)
 H5TB(0.5) C4TB(0.5) H4TB(0.5) C3TB(0.5) H3TB(0.5) C2TB(0.5) H2TB(0.5)
 C1SB(0.4) C1TA(0.5) C6TA(0.5) H6TA(0.5) C5TA(0.5) H5TA(0.5) C4TA(0.5)
 H4TA(0.5) C3TA(0.5) H3TA(0.5) C2TA(0.5) H2TA(0.5) C6SA(0.6) H6SA(0.6)
7.a Ternary CH refined with riding coordinates:
 C2C(H2C), C1DA(H1DA), C1DB(H1DB), C5DB(H5DB), C2DB(H2DB), C6DB(H6DB),
 C6C(H6C), C1C(H1C), C5C(H5C), C5DA(H5DA), C2DA(H2DA), C6DA(H6DA)
7.b Secondary CH2 refined with riding coordinates:
 C6A(H6AA,H6AB), C7A(H7AA,H7AB), C7B(H7BA,H7BB), C6B(H6BA,H6BB), C4C(H4CA,
 H4CB), C3C(H3CA,H3CB), C7DA(H7DA,H7DB), C3DA(H3DA,H3DB), C4DA(H4DA,H4DB),
 C8DB(H8DA,H8DB), C3DB(H3DC,H3DD), C4DB(H4DC,H4DD), C7DB(H7DC,H7DD), C8C(H8CA,
 H8CB), C7C(H7CA,H7CB), C8DA(H8DC,H8DD)
7.c Aromatic/amide H refined with riding coordinates:
 C1AA(H1AA), C2(H2), C4(H4), C0AA(H0AA), C9A(H9A), C8A(H8A), C3B(H3B),
 C5B(H5B), C10A(H10A), C9B(H9B), C10B(H10B), C4A(H4A), C5A(H5A), C4B(H4B),
 C15F(H15F), C16F(H16F), C43F(H43F), C3SA(H3SA), C5SA(H5SA), C2SA(H2SA),
 C4SA(H4SA), C12F(H12F), C2SB(H2SB), C3SB(H3SB), C4SB(H4SB), C5SB(H5SB),
 C6SB(H6SB), C13F(H13F), C6TB(H6TB), C5TB(H5TB), C4TB(H4TB), C3TB(H3TB),
 C2TB(H2TB), C45F(H45F), C44F(H44F), C14F(H14F), C46F(H46F), C6TA(H6TA),
 C5TA(H5TA), C4TA(H4TA), C3TA(H3TA), C2TA(H2TA), C42F(H42F), C6SA(H6SA),
 C12E(H12E), C13E(H13E), C14E(H14E), C15E(H15E), C16E(H16E), C24E(H24E),
 C25E(H25E), C26E(H26E), C42E(H42E), C43E(H43E), C44E(H44E), C45E(H45E),
 C46E(H46E), C32E(H32E), C33E(H33E), C34E(H34E), C35E(H35E), C36E(H36E),
 C23E(H23E), C22E(H22E)
7.d Fitted hexagon refined as free rotating group:
 C1SA(C2SB,C3SB,C4SB,C5SB,C6SB), C1TB(C6TB,C5TB,C4TB,C3TB,C2TB), C1TA(C6TA,
 C5TA,C4TA,C3TA,C2TA), C11E(C12E,C13E,C14E,C15E,C16E), C41E(C42E,C43E,C44E,C45E,
 C46E), C31E(C32E,C33E,C34E,C35E,C36E)
7.e Idealised Me refined as rotating group:
 C3DC(H3DE,H3DF,H3DG), C1DC(H1DC,H1DD,H1DE), C1AC(H1AB,H1AC,H1AD), C3AC(H3AA,
 H3AB,H3AC), C3BC(H3BA,H3BB,H3BC), C1BC(H1BA,H1BB,H1BC), C1EC(H1EA,H1EB,H1EC),
 C3EC(H3EA,H3EB,H3EC)
;
_shelx_res_checksum              76867
_shelx_hkl_checksum              70226
_olex2_submission_special_instructions 'No special instructions were received'