Reactions of Rh(PNP) pincer complexes with terminal alkynes: homocoupling through a ring or not at all.
Hood, Thomas M.; Chaplin, Adrian B.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 16649–16652; doi:10.1039/d0dt03550e

data_7705851
_publ_section_title
;
 Reactions of Rh(PNP) pincer complexes with terminal alkynes: homocoupling
 through a ring or not at all.
;
_journal_issue                   46
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16649
_journal_page_last               16652
_journal_paper_doi               10.1039/d0dt03550e
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C66 H118 N2 P4 Rh2, 2(C32 H12 B F24), C7 H8'
_chemical_formula_sum            'C137 H150 B2 F48 N2 P4 Rh2'
_chemical_formula_weight         3087.90
_chemical_melting_point          ?
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-27 deposited with the CCDC.	2020-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                114.303(2)
_cell_angle_beta                 91.2650(19)
_cell_angle_gamma                97.9770(18)
_cell_formula_units_Z            1
_cell_length_a                   15.3009(4)
_cell_length_b                   15.9126(3)
_cell_length_c                   16.7557(4)
_cell_measurement_reflns_used    21993
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4740
_cell_measurement_theta_min      2.8950
_cell_volume                     3667.92(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -92.00  -2.00   1.00    7.50    --  -41.82 125.00-180.00   90
  2  \w   -116.00 -17.00   1.00    7.50    --  -41.82 -37.00  30.00   99
  3  \w   -116.00 -17.00   1.00    7.50    --  -41.82 -37.00 120.00   99
  4  \w     23.00  98.00   1.00    7.50    --   41.82-125.00-180.00   75
  5  \w    -33.00  66.00   1.00    7.50    --   41.82 -37.00 -90.00   99
  6  \w     39.00 118.00   1.00    7.50    --   41.82-155.00  42.00   79
  7  \w     81.00 178.00   1.00   30.00    --  107.00  45.00-120.00   97
  8  \w     94.00 178.00   1.00   30.00    --  107.00 125.00  60.00   84
  9  \w     34.00 133.00   1.00   30.00    --  107.00 -45.00 -60.00   99
 10  \w     34.00 118.00   1.00   30.00    --  107.00-125.00 -30.00   84
 11  \w     34.00 118.00   1.00   30.00    --  107.00-125.00 -60.00   84
 12  \w     24.00 110.00   1.00   30.00    --  107.00 -94.00 -30.00   86
 13  \w     78.00 178.00   1.00   30.00    --  107.00  61.00-180.00  100
 14  \w     34.00 118.00   1.00   30.00    --  107.00-125.00 120.00   84
 15  \w     31.00 140.00   1.00   30.00    --  107.00 -77.00   0.00  109
 16  \w     94.00 178.00   1.00   30.00    --  107.00 125.00   0.00   84
 17  \w     81.00 178.00   1.00   30.00    --  107.00  45.00 150.00   97
 18  \w     81.00 178.00   1.00   30.00    --  107.00  45.00 -60.00   97
 19  \w     34.00 118.00   1.00   30.00    --  107.00-125.00 -90.00   84
 20  \w     34.00 118.00   1.00   30.00    --  107.00-125.00  30.00   84
 21  \w     81.00 178.00   1.00   30.00    --  107.00  45.00-180.00   97
 22  \w     34.00 118.00   1.00   30.00    --  107.00-125.00-180.00   84
 23  \w     35.00 136.00   1.00   30.00    --  107.00 -61.00 -30.00  101
 24  \w     34.00 118.00   1.00   30.00    --  107.00-125.00-120.00   84
 25  \w     34.00 118.00   1.00   30.00    --  107.00-125.00  60.00   84
 26  \w     94.00 178.00   1.00   30.00    --  107.00 125.00-150.00   84
 27  \w     81.00 178.00   1.00   30.00    --  107.00  45.00-150.00   97
 28  \w     35.00 136.00   1.00   30.00    --  107.00 -61.00  90.00  101
 29  \w   -114.00 -14.00   1.00    7.50    --  -41.82 -57.00   0.00  100
 30  \w   -118.00  -9.00   1.00    7.50    --  -41.82 -77.00 -60.00  109
 31  \w      1.00  83.00   1.00    7.50    --   41.82 -99.00  90.00   82
 32  \w      9.00 118.00   1.00    7.50    --   41.82  77.00 -60.00  109
 33  \w      9.00 118.00   1.00    7.50    --   41.82  77.00-150.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0828336000
_diffrn_orient_matrix_UB_12      -0.0070404000
_diffrn_orient_matrix_UB_13      0.0493948000
_diffrn_orient_matrix_UB_21      -0.0289270000
_diffrn_orient_matrix_UB_22      0.0680379000
_diffrn_orient_matrix_UB_23      0.0875190000
_diffrn_orient_matrix_UB_31      -0.0521385000
_diffrn_orient_matrix_UB_32      -0.0831311000
_diffrn_orient_matrix_UB_33      0.0125241000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0873
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            66659
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        70.068
_diffrn_reflns_theta_max         70.068
_diffrn_reflns_theta_min         6.402
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.186
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.288
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_density_meas      ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1578
_exptl_crystal_recrystallization_method
'Crystals grown from toluene/Et2O/pentane at 293 K'
_exptl_crystal_size_max          0.416
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.036
_refine_diff_density_max         1.264
_refine_diff_density_min         -0.618
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     954
_refine_ls_number_reflns         13931
_refine_ls_number_restraints     636
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0613
_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^)+(0.1057P)^2^+2.2322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1628
_refine_ls_wR_factor_ref         0.1781
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10941
_reflns_number_total             13931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03550e2.cif
_cod_data_source_block           0480abc19s
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        3667.91(15)
_cod_database_code               7705851
_shelx_shelxl_version_number     2014/7
_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
 C118-C117 \\sim C318-C117 \\sim C319-C318 \\sim C119-C118 \\sim C319-C120
\\sim C120-C119
 with sigma of 0.01
 C215-F7 \\sim C215-F8 \\sim C215-F9 \\sim C215-F7A \\sim C215-F8A \\sim
C215-F9A
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C211-F7 \\sim C211-F8 \\sim C211-F9 \\sim C211-F7A \\sim C211-F8A \\sim
C211-F9A
 with sigma of 0.01
 C216-F10 \\sim C216-F11 \\sim C216-F12 \\sim C216-F10A \\sim C216-F11A \\sim
C216-F12A
 with sigma of 0.01
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10A-F11A \\sim F11A-F12A \\sim
F12A-F10A
 with sigma of 0.01
 C213-F10 \\sim C213-F11 \\sim C213-F12 \\sim C213-F10A \\sim C213-F11A \\sim
C213-F12A
 with sigma of 0.01
 C223-F13 \\sim C223-F14 \\sim C223-F15 \\sim C223-F13A \\sim C223-F14A \\sim
C223-F15A
 with sigma of 0.01
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F13A-F14A \\sim F14A-F15A \\sim
F15A-F13A
 with sigma of 0.01
 C219-F13 \\sim C219-F14 \\sim C219-F15 \\sim C219-F13A \\sim C219-F14A \\sim
C219-F15A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C117 \\sim C118 \\sim C318 \\sim C119 \\sim C319 \\sim C120 \\sim C96 \\sim C90
\\sim C95 \\sim C94 \\sim C93 \\sim C92 \\sim C91 \\sim F1 \\sim F2 \\sim F3
\\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim
F9A \\sim F10 \\sim F10A \\sim F11 \\sim F11A \\sim F12 \\sim F12A \\sim F13
\\sim F13A \\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim F16 \\sim F17 \\sim
F18 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.014
Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C318) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C319) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C96)
\\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C94) \\sim Ueq,
Uanis(C93) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(F1)
\\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim Ueq,
Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim
Ueq, Uanis(F8) \\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F9A)
\\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F11A) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F14A) \\sim Ueq,
Uanis(F15) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq,
Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24)
\\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of 0.014
Uanis(F11) = Uanis(F11A)
Uanis(F12A) = Uanis(F12)
Uanis(F10) = Uanis(F10A)
Uanis(F7A) = Uanis(F7)
Uanis(F8) = Uanis(F8A)
Uanis(F9A) = Uanis(F9)
Uanis(F14A) = Uanis(F14)
Uanis(F15) = Uanis(F15A)
Uanis(F13A) = Uanis(F13)
4. Others
 Sof(H11U)=Sof(H11V)=Sof(H12C)=Sof(H12D)=Sof(C318)=Sof(H31A)=Sof(H31B)=
 Sof(C319)=Sof(H31C)=Sof(H31D)=1-FVAR(1)
 Sof(H11S)=Sof(H11T)=Sof(C118)=Sof(H11W)=Sof(H11X)=Sof(C119)=Sof(H11Y)=Sof(H)=
 Sof(H12A)=Sof(H12B)=FVAR(1)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(2)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
 Fixed Sof: C93(0.5) H93(0.5) C92(0.5) H92(0.5) C91(0.5) H91(0.5) C90(0.5)
 C95(0.5) H95(0.5) C94(0.5) H94(0.5) C96(0.5) H96A(0.5) H96B(0.5) H96C(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C107(H10A,H10B), C108(H10C,H10D), C117(H11S,H11T),
 C117(H11U,H11V), C118(H11W,H11X), C119(H11Y,H), C120(H12A,H12B), C120(H12C,
 H12D), C121(H12E,H12F), C122(H12G,H12H), C123(H12I,H12J), C124(H12K,H12L),
 C125(H12M,H12N), C126(H12O,H12P), C127(H12Q,H12R), C128(H12S,H12T), C129(H12U,
 H12V), C130(H13A,H13B), C318(H31A,H31B), C319(H31C,H31D)
5.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C105(H105), C202(H202), C204(H204), C206(H206),
 C210(H210), C212(H212), C214(H214), C218(H218), C220(H220), C222(H222),
 C226(H226), C228(H228), C230(H230), C93(H93), C92(H92), C91(H91), C95(H95),
 C94(H94)
5.d Fitted hexagon refined as free rotating group:
 C93(C92,C91,C90,C95,C94)
5.e Idealised Me refined as rotating group:
 C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C112(H11G,H11H,H11I), C114(H11J,
 H11K,H11L), C115(H11M,H11N,H11O), C116(H11P,H11Q,H11R), C96(H96A,H96B,H96C)
;
_shelx_res_checksum              20599
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 25.683
_oxdiff_exptl_absorpt_empirical_full_min 0.481