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_7705856
_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)'
_chemical_formula_sum            'C130 H142 B2 F48 N2 P4 Rh2'
_chemical_formula_weight         2995.77
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 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                90
_cell_angle_beta                 112.179(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.8941(5)
_cell_length_b                   16.1966(4)
_cell_length_c                   37.3543(8)
_cell_measurement_reflns_used    27601
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.6710
_cell_measurement_theta_min      3.3010
_cell_volume                     13386.6(6)
_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   -119.00  -5.00   1.00   10.00    --  -37.82 -37.00 -30.00  114
  2  \w    -72.00  42.00   1.00   10.00    --  -37.82  57.00-150.00  114
  3  \w   -126.00 -37.00   1.00   10.00    --  -37.82 178.00  90.00   89
  4  \w   -119.00 -32.00   1.00   10.00    --  -37.82 171.00 173.00   87
  5  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00 -90.00  114
  6  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00-150.00  114
  7  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00  90.00  114
  8  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00 -30.00  114
  9  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00   0.00  114
 10  \w    -71.00  43.00   1.00   10.00    --  -37.82  37.00 120.00  114
 11  \w   -118.00  -4.00   1.00   10.00    --  -37.82 -57.00 150.00  114
 12  \w     67.00 132.00   1.00   10.00    --   37.82 171.00 173.00   65
 13  \w    -42.00  72.00   1.00   10.00    --   37.82 -57.00 -30.00  114
 14  \w    104.00 178.00   1.00   40.00    --  112.00 111.00-180.00   74
 15  \w     29.00 109.00   1.00   40.00    --  112.00-111.00-120.00   80
 16  \w    103.00 178.00   1.00   40.00    --  112.00  77.00   0.00   75
 17  \w     25.00 149.00   1.00   40.00    --  112.00 -77.00  30.00  124
 18  \w     77.00 178.00   1.00   40.00    --  112.00  61.00 150.00  101
 19  \w     24.00 106.00   1.00   40.00    --  112.00 -94.00  90.00   82
 20  \w     24.00 106.00   1.00   40.00    --  112.00 -94.00 -90.00   82
 21  \w     77.00 178.00   1.00   40.00    --  112.00  61.00 120.00  101
 22  \w    104.00 178.00   1.00   40.00    --  112.00 111.00  60.00   74
 23  \w     77.00 178.00   1.00   40.00    --  112.00  61.00  90.00  101
 24  \w     77.00 178.00   1.00   40.00    --  112.00  61.00  60.00  101
 25  \w     79.00 178.00   1.00   40.00    --  112.00  45.00 -30.00   99
 26  \w     24.00 106.00   1.00   40.00    --  112.00 -94.00   0.00   82
 27  \w     79.00 178.00   1.00   40.00    --  112.00  45.00 -90.00   99
 28  \w     77.00 178.00   1.00   40.00    --  112.00  61.00-180.00  101
 29  \w     77.00 178.00   1.00   40.00    --  112.00  61.00   0.00  101
 30  \w     77.00 178.00   1.00   40.00    --  112.00  61.00-150.00  101
 31  \w     77.00 178.00   1.00   40.00    --  112.00  61.00  30.00  101
 32  \w     77.00 178.00   1.00   40.00    --  112.00  61.00-120.00  101
 33  \w     79.00 178.00   1.00   40.00    --  112.00  45.00 -60.00   99
 34  \w     29.00 109.00   1.00   40.00    --  112.00-111.00-150.00   80
 35  \w     77.00 126.00   1.00   40.00    --  112.00  61.00 -90.00   49
 36  \w     77.00 178.00   1.00   40.00    --  112.00  61.00 -30.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku Oxford Diffraction: SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0412034000
_diffrn_orient_matrix_UB_12      -0.0131570000
_diffrn_orient_matrix_UB_13      0.0427294000
_diffrn_orient_matrix_UB_21      0.0198484000
_diffrn_orient_matrix_UB_22      -0.0843087000
_diffrn_orient_matrix_UB_23      -0.0102377000
_diffrn_orient_matrix_UB_31      0.0524105000
_diffrn_orient_matrix_UB_32      0.0421273000
_diffrn_orient_matrix_UB_33      -0.0074108000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1043
_diffrn_reflns_av_unetI/netI     0.0642
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            99942
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.589
_diffrn_reflns_theta_max         66.589
_diffrn_reflns_theta_min         6.390
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.473
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.554
_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    1.486
_exptl_crystal_density_meas      ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             6112
_exptl_crystal_recrystallization_method
'Crystals grown from Et2O-SiMe4 at 293 K'
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.034
_refine_diff_density_max         2.044
_refine_diff_density_min         -3.317
_refine_diff_density_rms         0.184
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.43(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1898
_refine_ls_number_reflns         22577
_refine_ls_number_restraints     3977
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1978
_refine_ls_R_factor_gt           0.1755
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^+500.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3729
_refine_ls_wR_factor_ref         0.3884
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                17797
_reflns_number_total             22577
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03550e2.cif
_cod_data_source_block           0598abc20s
_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               7705856
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.57(3)
 0.43(3)
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
 C9-C8 \\sim C5-C4
 with sigma of 0.01
 C9-C10 \\sim C8-C7 \\sim C4-C11 \\sim C5-C6
 with sigma of 0.01
 C10-C11 \\sim C7-C6
 with sigma of 0.01
 P3-C113 \\sim P3-C130 \\sim P2-C109 \\sim P2-C117 \\sim P3-C108 \\sim P2-C107
\\sim P13-C230 \\sim P13-
 C208 \\sim P13-C213 \\sim P12-C217 \\sim P12-C207 \\sim P12-C209
 with sigma of 0.01
 C212-C209 \\sim C211-C209 \\sim C210-C209 \\sim C215-C213 \\sim C214-C213
\\sim C216-C213 \\sim C110-
 C109 \\sim C111-C109 \\sim C109-C112 \\sim C113-C116 \\sim C113-C114 \\sim
C113-C115
 with sigma of 0.01
 C108-C106 \\sim C107-C102 \\sim C208-C206 \\sim C202-C207
 with sigma of 0.01
 C130-C129 \\sim C128-C129 \\sim C128-C127 \\sim C127-C126 \\sim C125-C126
\\sim C125-C124 \\sim C123-
 C124 \\sim C122-C123 \\sim C122-C121 \\sim C121-C120 \\sim C119-C120 \\sim
C119-C118 \\sim C118-C117 ~
 C218-C217 \\sim C219-C218 \\sim C220-C219 \\sim C221-C220 \\sim C222-C221
\\sim C222-C223 \\sim C224-
 C223 \\sim C224-C225 \\sim C225-C226 \\sim C226-C227 \\sim C227-C228 \\sim
C228-C229 \\sim C230-C229
 with sigma of 0.01
 C117-C119 \\sim C118-C120 \\sim C119-C121 \\sim C120-C122 \\sim C121-C123
\\sim C122-C124 \\sim C123-
 C125 \\sim C124-C126 \\sim C125-C127 \\sim C126-C128 \\sim C127-C129 \\sim
C128-C130 \\sim C217-C219 ~
 C218-C220 \\sim C219-C221 \\sim C220-C222 \\sim C221-C223 \\sim C222-C224
\\sim C223-C225 \\sim C224-
 C226 \\sim C225-C227 \\sim C226-C228 \\sim C227-C229 \\sim C228-C230
 with sigma of 0.01
 C407-F401 \\sim C407-F402 \\sim C407-F403 \\sim C407-F501 \\sim C407-F502
\\sim C407-F503
 with sigma of 0.01
 F401-F402 \\sim F402-F403 \\sim F403-F401 \\sim F501-F502 \\sim F502-F503
\\sim F503-F501
 with sigma of 0.01
 C403-F401 \\sim C403-F402 \\sim C403-F403 \\sim C403-F501 \\sim C403-F502
\\sim C403-F503
 with sigma of 0.01
 C416-F410 \\sim C416-F411 \\sim C416-F412 \\sim C416-F510 \\sim C416-F511
\\sim C416-F512
 with sigma of 0.01
 F410-F411 \\sim F411-F412 \\sim F412-F410 \\sim F510-F511 \\sim F511-F512
\\sim F512-F510
 with sigma of 0.01
 C413-F410 \\sim C413-F411 \\sim C413-F412 \\sim C413-F510 \\sim C413-F511
\\sim C413-F512
 with sigma of 0.01
 C431-F419 \\sim C431-F420 \\sim C431-F421 \\sim C431-F519 \\sim C431-F520
\\sim C431-F521
 with sigma of 0.01
 F419-F420 \\sim F420-F421 \\sim F421-F419 \\sim F519-F520 \\sim F520-F521
\\sim F521-F519
 with sigma of 0.01
 C427-F419 \\sim C427-F420 \\sim C427-F421 \\sim C427-F519 \\sim C427-F520
\\sim C427-F521
 with sigma of 0.01
 C432-F422 \\sim C432-F423 \\sim C432-F424 \\sim C432-F522 \\sim C432-F523
\\sim C432-F524
 with sigma of 0.01
 F422-F423 \\sim F423-F424 \\sim F424-F422 \\sim F522-F523 \\sim F523-F524
\\sim F524-F522
 with sigma of 0.01
 C429-F422 \\sim C429-F423 \\sim C429-F424 \\sim C429-F522 \\sim C429-F523
\\sim C429-F524
 with sigma of 0.01
 C608-F604 \\sim C608-F605 \\sim C608-F606 \\sim C608-F704 \\sim C608-F705
\\sim C608-F706
 with sigma of 0.01
 F604-F605 \\sim F605-F606 \\sim F606-F604 \\sim F704-F705 \\sim F705-F706
\\sim F706-F704
 with sigma of 0.01
 C605-F604 \\sim C605-F605 \\sim C605-F606 \\sim C605-F704 \\sim C605-F705
\\sim C605-F706
 with sigma of 0.01
 C616-F610 \\sim C616-F611 \\sim C616-F612 \\sim C616-F710 \\sim C616-F711
\\sim C616-F712
 with sigma of 0.01
 F610-F611 \\sim F611-F612 \\sim F612-F610 \\sim F710-F711 \\sim F711-F712
\\sim F712-F710
 with sigma of 0.01
 C613-F610 \\sim C613-F611 \\sim C613-F612 \\sim C613-F710 \\sim C613-F711
\\sim C613-F712
 with sigma of 0.01
 C623-F613 \\sim C623-F614 \\sim C623-F615 \\sim C623-F713 \\sim C623-F714
\\sim C623-F715
 with sigma of 0.01
 F613-F614 \\sim F614-F615 \\sim F615-F613 \\sim F713-F714 \\sim F714-F715
\\sim F715-F713
 with sigma of 0.01
 C619-F613 \\sim C619-F614 \\sim C619-F615 \\sim C619-F713 \\sim C619-F714
\\sim C619-F715
 with sigma of 0.01
 C615-F607 \\sim C615-F608 \\sim C615-F609 \\sim C615-F707 \\sim C615-F708
\\sim C615-F709
 with sigma of 0.01
 F607-F608 \\sim F608-F609 \\sim F609-F607 \\sim F707-F708 \\sim F708-F709
\\sim F709-F707
 with sigma of 0.01
 C611-F607 \\sim C611-F608 \\sim C611-F609 \\sim C611-F707 \\sim C611-F708
\\sim C611-F709
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
5. Others
 Fixed Sof: F401(0.5) F402(0.5) F403(0.5) F410(0.5) F411(0.5) F412(0.5)
 F419(0.5) F420(0.5) F421(0.5) F422(0.5) F423(0.5) F424(0.5) F501(0.5)
 F502(0.5) F503(0.5) F510(0.5) F511(0.5) F512(0.5) F519(0.5) F520(0.5)
 F521(0.5) F522(0.5) F523(0.5) F524(0.5) F604(0.5) F605(0.5) F606(0.5)
 F607(0.5) F608(0.5) F609(0.5) F610(0.5) F611(0.5) F612(0.5) F613(0.5)
 F614(0.5) F615(0.5) F704(0.5) F705(0.5) F706(0.5) F707(0.5) F708(0.5)
 F709(0.5) F710(0.5) F711(0.5) F712(0.5) F713(0.5) F714(0.5) F715(0.5)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5), C8(H8), C9(H9)
6.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C10(H10A,H10B), C11(H11A,H11B), C107(H10C,H10D),
 C108(H10E,H10F), C117(H11U,H11V), C118(H11W,H11X), C119(H11Y,H), C120(H12A,
 H12B), C121(H12C,H12D), C122(H12E,H12F), C123(H12G,H12H), C124(H12I,H12J),
 C125(H12K,H12L), C126(H12M,H12N), C127(H12O,H12P), C128(H12Q,H12R), C129(H12S,
 H12T), C130(H13A,H13B), C207(H20A,H20B), C208(H20C,H20D), C217(H21S,H21T),
 C218(H21U,H21V), C219(H21W,H21X), C220(H22A,H22B), C221(H22C,H22D), C222(H22E,
 H22F), C223(H22G,H22H), C224(H22I,H22J), C225(H22K,H22L), C226(H22M,H22N),
 C227(H22O,H22P), C228(H22Q,H22R), C229(H22S,H22T), C230(H23A,H23B)
6.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C105(H105), C203(H203), C204(H204), C205(H205),
 C402(H402), C404(H404), C406(H406), C410(H410), C412(H412), C414(H414),
 C418(H418), C420(H420), C422(H422), C426(H426), C428(H428), C430(H430),
 C602(H602), C604(H604), C606(H606), C610(H610), C612(H612), C614(H614),
 C618(H618), C620(H620), C622(H622), C626(H626), C628(H628), C630(H630)
6.d Fitted hexagon refined as free rotating group:
 N101(C102,C103,C104,C105,C106), N201(C202,C203,C204,C205,C206)
6.e Idealised Me refined as rotating group:
 C110(H11C,H11D,H11E), C111(H11F,H11G,H11H), C112(H11I,H11J,H11K), C114(H11L,
 H11M,H11N), C115(H11O,H11P,H11Q), C116(H11R,H11S,H11T), C210(H21A,H21B,H21C),
 C211(H21D,H21E,H21F), C212(H21G,H21H,H21I), C214(H21J,H21K,H21L), C215(H21M,
 H21N,H21O), C216(H21P,H21Q,H21R)
;
_shelx_res_checksum              5025
_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 2.112
_oxdiff_exptl_absorpt_empirical_full_min 0.393