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_7705854
_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         'C29 H51 N P2 Rh, C32 H12 B F24, C7 H16'
_chemical_formula_sum            'C68 H79 B F24 N P2 Rh'
_chemical_formula_weight         1541.98
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-08-27
_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                90
_cell_angle_beta                 92.814(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9713(4)
_cell_length_b                   15.8991(3)
_cell_length_c                   25.1382(5)
_cell_measurement_reflns_used    15098
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.7080
_cell_measurement_theta_min      3.4920
_cell_volume                     7174.0(3)
_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    -70.00  41.00   1.00   11.00    --  -38.31  37.00 150.00  111
  2  \w      7.00 118.00   1.00   11.00    --   38.31  37.00-120.00  111
  3  \w    -21.00  74.00   1.00   11.00    --   38.31 -77.00 -60.00   95
  4  \w     61.00 131.00   1.00   11.00    --   38.31 178.00 150.00   70
  5  \w     24.00 107.00   1.00   50.00    --  111.00 -94.00 150.00   83
  6  \w    103.00 178.00   1.00   50.00    --  111.00  77.00  30.00   75
  7  \w    103.00 178.00   1.00   50.00    --  111.00  77.00 -90.00   75
  8  \w     61.00 146.00   1.00   50.00    --  111.00 178.00  60.00   85
  9  \w     33.00 144.00   1.00   50.00    --  111.00 -61.00 -60.00  111
 10  \w    103.00 178.00   1.00   50.00    --  111.00  77.00   0.00   75
 11  \w    103.00 178.00   1.00   50.00    --  111.00  77.00 -30.00   75
 12  \w    104.00 178.00   1.00   50.00    --  111.00 111.00  60.00   74
 13  \w     61.00 146.00   1.00   50.00    --  111.00 178.00 150.00   85
 14  \w   -116.00  -6.00   1.00   11.00    --  -38.31 -57.00  30.00  110
 15  \w   -116.00  -6.00   1.00   11.00    --  -38.31 -57.00 120.00  110
 16  \w     58.00 129.00   1.00   11.00    --   38.31-178.00 -60.00   71
 17  \w      6.00 116.00   1.00   11.00    --   38.31  57.00 -30.00  110
 18  \w     80.00 178.00   1.00   50.00    --  111.00  45.00-120.00   98
 19  \w     78.00 178.00   1.00   50.00    --  111.00  61.00  90.00  100
 20  \w     80.00 178.00   1.00   50.00    --  111.00  45.00 150.00   98
 21  \w     78.00 171.00   1.00   50.00    --  111.00  61.00-180.00   93
 22  \w     78.00 178.00   1.00   50.00    --  111.00  61.00 -60.00  100
;
_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      -0.0226605000
_diffrn_orient_matrix_UB_12      -0.0677283000
_diffrn_orient_matrix_UB_13      0.0399458000
_diffrn_orient_matrix_UB_21      0.0602729000
_diffrn_orient_matrix_UB_22      0.0322586000
_diffrn_orient_matrix_UB_23      0.0406576000
_diffrn_orient_matrix_UB_31      -0.0566983000
_diffrn_orient_matrix_UB_32      0.0613762000
_diffrn_orient_matrix_UB_33      0.0227215000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            21894
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.594
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         6.365
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.256
_exptl_absorpt_correction_T_max  0.835
_exptl_absorpt_correction_T_min  0.586
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.428
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             3160
_exptl_crystal_recrystallization_method 'Crystals grown from heptane at 278 K'
_exptl_crystal_size_max          0.222
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.07
_refine_diff_density_max         3.226
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1057
_refine_ls_number_reflns         21894
_refine_ls_number_restraints     1023
_refine_ls_restrained_S_all      1.159
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0689
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1328P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1888
_refine_ls_wR_factor_ref         0.1968
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16487
_reflns_number_total             21894
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9906\% 
around [1.00 0.00 -0.00] (reciprocal) or [1.00 0.00 0.03] (direct)
;
_cod_data_source_file            d0dt03550e2.cif
_cod_data_source_block           0603abc20s
_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_database_code               7705854
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6357(11)
 0.3643(11)
2. 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
3. Restrained distances
 C220-C119 \\sim C120-C119
 with sigma of 0.01
 C221-C220 \\sim C121-C120
 with sigma of 0.01
 C221-C122 \\sim C122-C121
 with sigma of 0.01
 P2-C117 \\sim P2-C217
 with sigma of 0.01
 C218-C217 \\sim C118-C117
 with sigma of 0.01
 C119-C118 \\sim C218-C119
 with sigma of 0.01
 C124-C123 \\sim C224-C123 \\sim C124-C125 \\sim C125-C224
 with sigma of 0.01
 C415-F7 \\sim C415-F8 \\sim C415-F9 \\sim C415-F7A \\sim C415-F8A \\sim
C415-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
 C411-F7 \\sim C411-F8 \\sim C411-F9 \\sim C411-F7A \\sim C411-F8A \\sim
C411-F9A
 with sigma of 0.01
 C416-F10 \\sim C416-F11 \\sim C416-F12 \\sim C416-F10A \\sim C416-F11A \\sim
C416-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
 C413-F10 \\sim C413-F11 \\sim C413-F12 \\sim C413-F10A \\sim C413-F11A \\sim
C413-F12A
 with sigma of 0.01
 C423-F13 \\sim C423-F14 \\sim C423-F15 \\sim C423-F13A \\sim C423-F14A \\sim
C423-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
 C419-F13 \\sim C419-F14 \\sim C419-F15 \\sim C419-F13A \\sim C419-F14A \\sim
C419-F15A
 with sigma of 0.01
 C424-F16 \\sim C424-F17 \\sim C424-F18 \\sim C424-F16A \\sim C424-F17A \\sim
C424-F18A
 with sigma of 0.01
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F16A-F17A \\sim F17A-F18A \\sim
F18A-F16A
 with sigma of 0.01
 C421-F16 \\sim C421-F17 \\sim C421-F18 \\sim C421-F16A \\sim C421-F17A \\sim
C421-F18A
 with sigma of 0.01
 C432-F22 \\sim C432-F23 \\sim C432-F24 \\sim C432-F22A \\sim C432-F23A \\sim
C432-F24A
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.01
 C429-F22 \\sim C429-F23 \\sim C429-F24 \\sim C429-F22A \\sim C429-F23A \\sim
C429-F24A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C217 \\sim C117 \\sim C118 \\sim C218 \\sim C119 \\sim C120 \\sim C220 \\sim
C121 \\sim C221 \\sim C122 \\sim C123 \\sim C224 \\sim C124 \\sim C125 \\sim
C126 \\sim C127 \\sim C901 \\sim C902 \\sim C903 \\sim C904 \\sim C905 \\sim
C906 \\sim C907 \\sim C432 \\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 F16A \\sim F17 \\sim F17A \\sim
F18 \\sim F18A \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F22A \\sim F23
\\sim F23A \\sim F24 \\sim F24A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C217) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C218) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C220) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C221) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C224) \\sim Ueq,
Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(C432) \\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(F16A) \\sim Ueq,
Uanis(F17) \\sim Ueq, Uanis(F17A) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F18A)
\\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq,
Uanis(F22) \\sim Ueq, Uanis(F22A) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F23A)
\\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F24A) \\sim Ueq: with sigma of 0.006 and
sigma for terminal atoms of 0.012
Uanis(C901) \\sim Ueq, Uanis(C902) \\sim Ueq, Uanis(C903) \\sim Ueq,
Uanis(C904) \\sim Ueq, Uanis(C905) \\sim Ueq, Uanis(C906) \\sim Ueq,
Uanis(C907) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C120) = Uanis(C220)
Uanis(C224) = Uanis(C124)
5. Others
 Sof(H11W)=Sof(H12E)=Sof(H12F)=Sof(H12I)=Sof(H12J)=Sof(H12O)=Sof(H12P)=
 Sof(C217)=Sof(H21A)=Sof(H21B)=Sof(C218)=Sof(H21C)=Sof(H21D)=Sof(C220)=
 Sof(H220)=Sof(C221)=Sof(H22A)=Sof(H22B)=Sof(C224)=Sof(H22C)=Sof(H22D)=1-FVAR(1)
 Sof(C117)=Sof(H11S)=Sof(H11T)=Sof(C118)=Sof(H11U)=Sof(H11V)=Sof(H119)=
 Sof(C120)=Sof(H120)=Sof(C121)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(H12D)=
 Sof(H12G)=Sof(H12H)=Sof(C124)=Sof(H12K)=Sof(H12L)=Sof(H12M)=Sof(H12N)=FVAR(1)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(2)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(2)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(3)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(4)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(4)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(5)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(5)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(6)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C119(H119), C119(H11W), C120(H120), C220(H220)
6.b Secondary CH2 refined with riding coordinates:
 C107(H10A,H10B), C108(H10C,H10D), C117(H11S,H11T), C118(H11U,H11V), C121(H12A,
 H12B), C122(H12C,H12D), C122(H12E,H12F), C123(H12I,H12J), C123(H12G,H12H),
 C124(H12K,H12L), C125(H12O,H12P), C125(H12M,H12N), C126(H12Q,H12R), C127(H12S,
 H12T), C128(H12U,H12V), C129(H12W,H12X), C130(H13A,H13B), C217(H21A,H21B),
 C218(H21C,H21D), C221(H22A,H22B), C224(H22C,H22D), C902(H90D,H90E), C903(H90F,
 H90G), C904(H90H,H90I), C905(H90J,H90K), C906(H90L,H90M)
6.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C105(H105), C402(H402), C404(H404), C406(H406),
 C410(H410), C412(H412), C414(H414), C418(H418), C420(H420), C422(H422),
 C426(H426), C428(H428), C430(H430)
6.d 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), C901(H90A,H90B,H90C),
 C907(H90N,H90O,H90P)
;
_shelx_res_checksum              70212
_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 3.322
_oxdiff_exptl_absorpt_empirical_full_min 0.492
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2