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_7705853
_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         'C35 H63 N P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C67 H75 B F24 N P2 Rh'
_chemical_formula_weight         1525.94
_chemical_melting_point          ?
_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'
_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                 114.030(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.1438(6)
_cell_length_b                   13.3315(3)
_cell_length_c                   26.4445(8)
_cell_measurement_reflns_used    12974
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.1700
_cell_measurement_theta_min      3.3360
_cell_volume                     7130.1(4)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -114.00 -14.00   1.00   30.00    --  -41.82 -57.00 -90.00  100
  2  \w    -66.00  33.00   1.00   30.00    --  -41.82  37.00-120.00   99
  3  \w   -117.00 -56.00   1.00   30.00    --  -41.82-156.00-142.00   61
  4  \w    -21.00  74.00   1.00   30.00    --   41.82 -77.00  30.00   95
  5  \w     97.00 178.00   1.00  130.00    --  107.00 125.00-120.00   81
  6  \w    103.00 178.00   1.00  130.00    --  107.00  77.00 -90.00   75
  7  \w     97.00 178.00   1.00  130.00    --  107.00 125.00 150.00   81
  8  \w    103.00 178.00   1.00  130.00    --  107.00  77.00-120.00   75
  9  \w     78.00 178.00   1.00  130.00    --  107.00  61.00 -30.00  100
 10  \w    103.00 178.00   1.00  130.00    --  107.00  77.00  30.00   75
 11  \w     31.00 140.00   1.00  130.00    --  107.00 -77.00 -90.00  109
 12  \w     78.00 178.00   1.00  130.00    --  107.00  61.00   0.00  100
 13  \w     31.00 140.00   1.00  130.00    --  107.00 -77.00  90.00  109
 14  \w     78.00 178.00   1.00  130.00    --  107.00  61.00 -60.00  100
 15  \w   -114.00 -45.00   1.00   30.00    --  -41.82 -57.00 120.00   69
;
_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      0.0190736000
_diffrn_orient_matrix_UB_12      -0.0748449000
_diffrn_orient_matrix_UB_13      -0.0353730000
_diffrn_orient_matrix_UB_21      -0.0413377000
_diffrn_orient_matrix_UB_22      0.0602083000
_diffrn_orient_matrix_UB_23      -0.0524955000
_diffrn_orient_matrix_UB_31      0.0610909000
_diffrn_orient_matrix_UB_32      0.0642070000
_diffrn_orient_matrix_UB_33      0.0079755000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0823
_diffrn_reflns_av_unetI/netI     0.0644
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            55466
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        70.068
_diffrn_reflns_theta_max         70.068
_diffrn_reflns_theta_min         6.330
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.271
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.340
_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            purple
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_density_meas      ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             3120
_exptl_crystal_recrystallization_method
'Crystals grown from Et2O-SiMe4 at 278 K'
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.011
_refine_diff_density_max         1.065
_refine_diff_density_min         -1.452
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1084
_refine_ls_number_reflns         13524
_refine_ls_number_restraints     1299
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0983
_refine_ls_R_factor_gt           0.0795
_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^)+(0.1419P)^2^+3.7266P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2220
_refine_ls_wR_factor_ref         0.2494
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10003
_reflns_number_total             13524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03550e2.cif
_cod_data_source_block           0600abc20s
_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               7705853
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C129-C130 \\sim C128-C129 \\sim C127-C128 \\sim C127-C126 \\sim C125-C126
\\sim C125-C124 \\sim C123-
 C124 \\sim C122-C123 \\sim C121-C122 \\sim C121-C120 \\sim C119-C120 \\sim
C119-C118 \\sim C118-C117
 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
 with sigma of 0.01
 C217-C218 \\sim C218-C219 \\sim C219-C220 \\sim C220-C221 \\sim C221-C222
\\sim C223-C222 \\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
 C217-C219 \\sim 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
 P3-C230 \\sim P3-C130 \\sim P2-C217 \\sim P2-C117
 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
 C423-F413 \\sim C423-F414 \\sim C423-F415 \\sim C423-F513 \\sim C423-F514
\\sim C423-F515
 with sigma of 0.01
 F413-F414 \\sim F414-F415 \\sim F415-F413 \\sim F513-F514 \\sim F514-F515
\\sim F515-F513
 with sigma of 0.01
 C419-F413 \\sim C419-F414 \\sim C419-F415 \\sim C419-F513 \\sim C419-F514
\\sim C419-F515
 with sigma of 0.01
 C424-F416 \\sim C424-F417 \\sim C424-F418 \\sim C424-F516 \\sim C424-F517
\\sim C424-F518
 with sigma of 0.01
 F416-F417 \\sim F417-F418 \\sim F418-F416 \\sim F516-F517 \\sim F517-F518
\\sim F518-F516
 with sigma of 0.01
 C421-F416 \\sim C421-F417 \\sim C421-F418 \\sim C421-F516 \\sim C421-F517
\\sim C421-F518
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C130 \\sim C117 \\sim C129 \\sim C118 \\sim C124 \\sim C120 \\sim C128 \\sim
C123 \\sim C121 \\sim C122 \\sim C119 \\sim C125 \\sim C127 \\sim C126 \\sim
C218 \\sim C219 \\sim C228 \\sim C225 \\sim C227 \\sim C220 \\sim C221 \\sim
C222 \\sim C224 \\sim C226 \\sim C229 \\sim C217 \\sim C223 \\sim C230 \\sim
C423 \\sim F401 \\sim F402 \\sim F403 \\sim F404 \\sim F405 \\sim F406 \\sim
F407 \\sim F408 \\sim F409 \\sim F410 \\sim F411 \\sim F412 \\sim F413 \\sim
F414 \\sim F415 \\sim F416 \\sim F417 \\sim F418 \\sim F419 \\sim F420 \\sim
F421 \\sim F422 \\sim F423 \\sim F424 \\sim F510 \\sim F511 \\sim F512 \\sim
F513 \\sim F514 \\sim F515 \\sim F516 \\sim F517 \\sim F518: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C130) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C129) \\sim Ueq,
Uanis(C118) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C128) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C121) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C125) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C218) \\sim Ueq,
Uanis(C219) \\sim Ueq, Uanis(C228) \\sim Ueq, Uanis(C225) \\sim Ueq,
Uanis(C227) \\sim Ueq, Uanis(C220) \\sim Ueq, Uanis(C221) \\sim Ueq,
Uanis(C222) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C226) \\sim Ueq,
Uanis(C229) \\sim Ueq, Uanis(C217) \\sim Ueq, Uanis(C223) \\sim Ueq,
Uanis(C230) \\sim Ueq, Uanis(C423) \\sim Ueq, Uanis(F401) \\sim Ueq,
Uanis(F402) \\sim Ueq, Uanis(F403) \\sim Ueq, Uanis(F404) \\sim Ueq,
Uanis(F405) \\sim Ueq, Uanis(F406) \\sim Ueq, Uanis(F407) \\sim Ueq,
Uanis(F408) \\sim Ueq, Uanis(F409) \\sim Ueq, Uanis(F410) \\sim Ueq,
Uanis(F411) \\sim Ueq, Uanis(F412) \\sim Ueq, Uanis(F413) \\sim Ueq,
Uanis(F414) \\sim Ueq, Uanis(F415) \\sim Ueq, Uanis(F416) \\sim Ueq,
Uanis(F417) \\sim Ueq, Uanis(F418) \\sim Ueq, Uanis(F419) \\sim Ueq,
Uanis(F420) \\sim Ueq, Uanis(F421) \\sim Ueq, Uanis(F422) \\sim Ueq,
Uanis(F423) \\sim Ueq, Uanis(F424) \\sim Ueq, Uanis(F510) \\sim Ueq,
Uanis(F511) \\sim Ueq, Uanis(F512) \\sim Ueq, Uanis(F513) \\sim Ueq,
Uanis(F514) \\sim Ueq, Uanis(F515) \\sim Ueq, Uanis(F516) \\sim Ueq,
Uanis(F517) \\sim Ueq, Uanis(F518) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Sof(C217)=Sof(H21A)=Sof(H21B)=Sof(C218)=Sof(H21C)=Sof(H21D)=Sof(C219)=
 Sof(H21E)=Sof(H21F)=Sof(C220)=Sof(H22A)=Sof(H22B)=Sof(C221)=Sof(H22C)=
 Sof(H22D)=Sof(C222)=Sof(H22E)=Sof(H22F)=Sof(C223)=Sof(H22G)=Sof(H22H)=
 Sof(C224)=Sof(H22I)=Sof(H22J)=Sof(C225)=Sof(H22K)=Sof(H22L)=Sof(C226)=
 Sof(H22M)=Sof(H22N)=Sof(C227)=Sof(H22O)=Sof(H22P)=Sof(C228)=Sof(H22Q)=
 Sof(H22R)=Sof(C229)=Sof(H22S)=Sof(H22T)=Sof(C230)=Sof(H23A)=Sof(H23B)=1-FVAR(1)
 Sof(C117)=Sof(H11S)=Sof(H11T)=Sof(C118)=Sof(H11U)=Sof(H11V)=Sof(C119)=
 Sof(H11W)=Sof(H11X)=Sof(C120)=Sof(H12A)=Sof(H12B)=Sof(C121)=Sof(H12C)=
 Sof(H12D)=Sof(C122)=Sof(H12E)=Sof(H12F)=Sof(C123)=Sof(H12G)=Sof(H12H)=
 Sof(C124)=Sof(H12I)=Sof(H12J)=Sof(C125)=Sof(H12K)=Sof(H12L)=Sof(C126)=
 Sof(H12M)=Sof(H12N)=Sof(C127)=Sof(H12O)=Sof(H12P)=Sof(C128)=Sof(H12Q)=
 Sof(H12R)=Sof(C129)=Sof(H12S)=Sof(H12T)=Sof(C130)=Sof(H13A)=Sof(H13B)=FVAR(1)
 Sof(F516)=Sof(F517)=Sof(F518)=1-FVAR(2)
 Sof(F416)=Sof(F417)=Sof(F418)=FVAR(2)
 Sof(F510)=Sof(F511)=Sof(F512)=1-FVAR(3)
 Sof(F410)=Sof(F411)=Sof(F412)=FVAR(3)
 Fixed Sof: F413(0.5) F414(0.5) F415(0.5) F513(0.5) F514(0.5) F515(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C107(H10A,H10B), C108(H10C,H10D), C117(H11S,H11T), C118(H11U,H11V), C119(H11W,
 H11X), 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), C217(H21A,H21B), C218(H21C,H21D),
 C219(H21E,H21F), 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)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), 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)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C110(H11A,H11B,H11C),
 C111(H11D,H11E,H11F), C112(H11G,H11H,H11I), C114(H11J,H11K,H11L), C115(H11M,
 H11N,H11O), C116(H11P,H11Q,H11R)
;
_shelx_res_checksum              39694
_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 19.583
_oxdiff_exptl_absorpt_empirical_full_min 0.379