Induced <i>fac</i>-<i>mer</i> rearrangements in {M(CO)<sub>3</sub>}<sup>+</sup> complexes (M = Re, <sup>99(m)</sup>Tc) by a PNP ligand.
Besmer, Manuel Luca; Schwitter, Flurina; Battistin, Federica; Braband, Henrik; Fox, Thomas; Spingler, Bernhard; Alberto, Roger; Dalton transactions (Cambridge, England : 2003) 53 (2024) 1434–1438; doi:10.1039/d3dt03992g

data_7714873
_publ_section_title
;
 Induced <i>fac</i>-<i>mer</i> rearrangements in
 {M(CO)<sub>3</sub>}<sup>+</sup> complexes (M = Re, <sup>99(m)</sup>Tc) by
 a PNP ligand.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1434
_journal_page_last               1438
_journal_paper_doi               10.1039/d3dt03992g
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'2(C26 H43 N O3 P2 Re), 2.053(B0.95 F3.8), 0.05(Br)'
_chemical_formula_sum            'C52 H86 B1.95 Br0.05 F7.8 N2 O6 P4 Re2'
_chemical_formula_weight         1504.78
_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
_audit_creation_date             2023-10-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2023-11-13 deposited with the CCDC.	2023-12-28 downloaded from the CCDC.
;
_cell_angle_alpha                85.4844(7)
_cell_angle_beta                 89.7211(6)
_cell_angle_gamma                89.6147(8)
_cell_formula_units_Z            2
_cell_length_a                   8.87921(7)
_cell_length_b                   12.57039(13)
_cell_length_c                   27.5441(2)
_cell_measurement_reflns_used    70456
_cell_measurement_temperature    159.99(10)
_cell_measurement_theta_max      79.1670
_cell_measurement_theta_min      3.2090
_cell_volume                     3064.70(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      159.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.965
_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    -87.00 -30.00   0.50    2.00    --  -50.12 -69.00 -69.00  114
  2  \w    -21.00  14.00   0.50    2.00    --   50.12 -69.00 -69.00   70
  3  \w     19.00  58.00   0.50    2.00    --   50.12 -69.00 -69.00   78
  4  \w     30.00  67.00   0.50    2.00    --   50.12  69.00  63.00   74
  5  \w    -94.00 -68.00   0.50    5.00    --  -88.50 -69.00 -69.00   52
  6  \w     90.00 126.00   0.50    5.00    --  110.00  69.00  63.00   72
  7  \w    101.00 127.00   0.50    5.00    --  110.00 -69.00 -69.00   52
  8  \w     39.00  67.00   0.50    5.00    --  110.00 -69.00 -69.00   56
  9  \w      3.00  43.00   0.50    2.00    --    8.00-101.00-111.02   80
 10  \w     -6.00  19.00   0.50    2.00    --   20.00  84.00 -60.43   50
 11  \w      1.00  26.00   0.50    2.00    --   24.00  75.00 -96.51   50
 12  \w      8.00  33.00   0.50    2.00    --   28.00  69.00   9.72   50
 13  \w    -38.00 -13.00   0.50    2.00    --  -32.00 -65.00 -50.91   50
 14  \w    -45.00 -18.00   0.50    2.00    --  -36.00 -62.00 158.08   54
 15  \w    -44.00 -18.00   0.50    2.00    --  -36.00 -63.00-169.52   52
 16  \w     18.00  43.00   0.50    2.00    --   36.00  63.00-122.21   50
 17  \w    -50.00 -25.00   0.50    2.00    --  -40.00 -60.00  88.66   50
 18  \w     23.00  48.00   0.50    2.00    --   40.00  60.00 152.35   50
 19  \w     23.00  48.00   0.50    2.00    --   40.00  59.00  55.17   50
 20  \w    -61.00 -35.00   0.50    2.00    --  -48.00 -56.00-150.63   52
 21  \w    -62.00 -32.00   0.50    2.00    --  -48.00 -56.00 133.80   60
 22  \w   -120.00 -74.00   0.50    2.00    --  -48.00 -56.00 133.80   92
 23  \w   -102.00 -38.00   0.50    2.00    --  -50.12 -19.00-120.00  128
 24  \w    -50.00  13.00   0.50    2.00    --  -50.12  69.00  63.00  126
 25  \w     34.00  97.00   0.50    2.00    --   50.12-125.00 -90.00  126
 26  \w    -80.00 -36.00   0.50    2.00    --  -52.00 -56.00   7.52   88
 27  \w   -114.00 -85.00   0.50    2.00    --  -52.00 -56.00   7.52   58
 28  \w    -72.00 -36.00   0.50    2.00    --  -52.00 -56.00-176.91   72
 29  \w    -86.00 -44.00   0.50    2.00    --  -60.00 -55.00  94.05   84
 30  \w    -83.00 -45.00   0.50    2.00    --  -60.00 -55.00  69.47   76
 31  \w   -133.00 -97.00   0.50    2.00    --  -60.00 -55.00  69.47   72
 32  \w    -73.00 -48.00   0.50    2.00    --  -64.00 -54.00-123.49   50
 33  \w    -83.00 -48.00   0.50    2.00    --  -64.00 -54.00 -41.02   70
 34  \w    -76.00 -48.00   0.50    2.00    --  -64.00 -54.00 125.98   56
 35  \w   -133.00-106.00   0.50    2.00    --  -64.00 -54.00-123.49   54
 36  \w    -80.00 -54.00   0.50    2.00    --  -68.00 -54.00 156.70   52
 37  \w    -81.00 -56.00   0.50    2.00    --  -72.00 -55.00 173.45   50
 38  \w   -142.00-116.00   0.50    2.00    --  -72.00 -55.00 173.45   52
 39  \w    -87.00 -58.00   0.50    2.00    --  -72.00 -55.00  63.60   58
 40  \w    -86.00 -61.00   0.50    2.00    --  -76.00 -52.00 -20.40   50
 41  \w    -87.00 -61.00   0.50    2.00    --  -76.00 -56.00  17.40   52
 42  \w   -142.00-117.00   0.50    2.00    --  -76.00 -55.00  83.88   50
 43  \w    -85.00 -60.00   0.50    2.00    --  -76.00 -55.00  83.88   50
 44  \w    -85.00 -60.00   0.50    2.00    --  -76.00 -56.00-134.73   50
 45  \w    -97.00 -67.00   0.50    2.00    --  -80.00 -56.00  43.98   60
 46  \w    -95.00 -64.00   0.50    2.00    --  -80.00 -55.00-146.33   62
 47  \w    -90.00 -64.00   0.50    2.00    --  -80.00 -56.00 109.39   52
 48  \w    -91.00 -65.00   0.50    2.00    --  -80.00 -56.00 137.40   52
 49  \w    -92.00 -64.00   0.50    2.00    --  -80.00 -54.00 -67.03   56
 50  \w   -153.00-126.00   0.50    2.00    --  -80.00 -55.00-146.33   54
 51  \w    -95.00 -64.00   0.50    2.00    --  -80.00 -56.00   6.28   62
 52  \w    -89.00 -64.00   0.50    2.00    --  -80.00 -56.00 -84.25   50
 53  \w    -99.00 -64.00   0.50    2.00    --  -80.00 -56.00 -48.08   70
 54  \w    -90.00 -64.00   0.50    2.00    --  -80.00 -56.00-162.54   52
 55  \w    -91.00 -65.00   0.50    2.00    --  -80.00 -56.00  52.75   52
 56  \w    -93.00 -68.00   0.50    5.00    --  -84.00 -55.00 148.31   50
 57  \w    -98.00 -73.00   0.50    5.00    --  -88.50 -55.00-154.89   50
 58  \w   -162.00 -73.00   0.50    5.00    --  -88.50 -55.00 -12.75  178
 59  \w   -119.00 -73.00   0.50    5.00    --  -88.50 -55.00  36.36   92
 60  \w   -110.00 -74.00   0.50    5.00    --  -88.50 -55.00-120.40   72
 61  \w   -160.00-116.00   0.50    5.00    --  -88.50 -55.00-120.40   88
 62  \w   -104.00 -73.00   0.50    5.00    --  -88.50 -55.00 103.55   62
 63  \w   -161.00-135.00   0.50    5.00    --  -88.50 -55.00 103.55   52
 64  \w    -99.00 -73.00   0.50    5.00    --  -88.50 -55.00 130.78   52
 65  \w   -100.00 -74.00   0.50    5.00    --  -88.50 -54.00  81.58   52
 66  \w    -98.00 -73.00   0.50    5.00    --  -88.50 -55.00   7.86   50
 67  \w   -100.00 -74.00   0.50    5.00    --  -88.50 -55.00 176.25   52
 68  \w   -104.00 -78.00   0.50    5.00    --  -88.50 -56.00 171.64   52
 69  \w    -98.00 -73.00   0.50    5.00    --  -88.50 -54.00-108.88   50
 70  \w   -105.00 -73.00   0.50    5.00    --  -88.50 -53.00 -33.54   64
 71  \w   -100.00 -73.00   0.50    5.00    --  -88.50 -55.00-172.52   54
 72  \w    -99.00 -73.00   0.50    5.00    --  -88.50 -54.00 106.56   52
 73  \w    -87.00 -61.00   0.50    5.00    --  -88.50  69.00  63.00   52
 74  \w     40.00  72.00   0.50    5.00    --  110.00 -61.00  30.00   64
 75  \w     98.00 154.00   0.50    5.00    --  110.00  45.00-180.00  112
 76  \w     93.00 126.00   0.50    5.00    --  110.00  61.00 120.00   66
 77  \w     54.00 123.00   0.50    5.00    --  110.00 -45.00-150.00  138
 78  \w    100.00 167.00   0.50    5.00    --  110.00  45.00-150.00  134
 79  \w    136.00 177.00   0.50    5.00    --  110.00  45.00  30.00   82
 80  \w    100.00 131.00   0.50    5.00    --  110.00  45.00  30.00   62
 81  \w    136.00 175.00   0.50    5.00    --  110.00  45.00 -60.00   78
 82  \w     34.00  64.00   0.50    5.00    --  110.00 -94.00 -60.00   60
 83  \w     96.00 122.00   0.50    5.00    --  110.00  45.00 -60.00   52
 84  \w     37.00 108.00   0.50    5.00    --  110.00-111.00-150.00  142
 85  \w    143.00 169.00   0.50    5.00    --  110.00  61.00  60.00   52
 86  \w     93.00 119.00   0.50    5.00    --  110.00  61.00  60.00   52
 87  \w     43.00 107.00   0.50    5.00    --  110.00 -94.00 -90.00  128
 88  \w     72.00 107.00   0.50    5.00    --  110.00 -94.00  90.00   70
 89  \w     37.00  65.00   0.50    5.00    --  110.00 -94.00  90.00   56
 90  \w    143.00 178.00   0.50    5.00    --  110.00  61.00-120.00   70
 91  \w     93.00 170.00   0.50    5.00    --  110.00  61.00  90.00  154
 92  \w     94.00 135.00   0.50    5.00    --  110.00  61.00-120.00   82
 93  \w    105.00 175.00   0.50    5.00    --  110.00  77.00 -90.00  140
 94  \w     93.00 146.00   0.50    5.00    --  110.00  61.00 -30.00  106
 95  \w     93.00 142.00   0.50    5.00    --  110.00  61.00-150.00   98
 96  \w     78.00 107.00   0.50    5.00    --  110.00 -94.00 120.00   58
 97  \w     93.00 137.00   0.50    5.00    --  110.00  61.00  30.00   88
 98  \w     44.00 108.00   0.50    5.00    --  110.00-111.00 -90.00  128
 99  \w     46.00  71.00   0.50    5.00    --  110.00 -94.00 120.00   50
100  \w    109.00 134.00   0.50    5.00    --  110.00 -77.00 120.00   50
101  \w     42.00  91.00   0.50    5.00    --  110.00 -77.00 120.00   98
102  \w     93.00 142.00   0.50    5.00    --  110.00  61.00 -90.00   98
103  \w     74.00 122.00   0.50    5.00    --  110.00 -30.00 120.00   96
104  \w    101.00 148.00   0.50    5.00    --  110.00  45.00 120.00   94
105  \w    149.00 177.00   0.50    5.00    --  110.00  55.00 -11.32   56
106  \w     73.00 108.00   0.50    5.00    --  110.00-111.00  90.00   70
107  \w     31.00  59.00   0.50    5.00    --  110.00 -30.00 120.00   56
108  \w     35.00 105.00   0.50    5.00    --  110.00 -45.00 -60.00  140
109  \w    101.00 127.00   0.50    5.00    --  110.00 -61.00 120.00   52
110  \w     94.00 145.00   0.50    5.00    --  110.00  55.00 -11.32  102
111  \w     39.00  86.00   0.50    5.00    --  110.00 -61.00 120.00   94
112  \w     93.00 177.00   0.50    5.00    --  110.00  59.00  46.01  168
113  \w     39.00 108.00   0.50    5.00    --  110.00-111.00  30.00  138
114  \w     38.00  69.00   0.50    5.00    --  110.00 -77.00  90.00   62
115  \w     84.00 109.00   0.50    5.00    --  110.00 -77.00  90.00   50
116  \w     37.00  63.00   0.50    5.00    --  110.00-111.00  90.00   52
117  \w    137.00 173.00   0.50    5.00    --  110.00  77.00-180.00   72
118  \w    101.00 129.00   0.50    5.00    --  110.00  77.00-180.00   56
119  \w    145.00 174.00   0.50    5.00    --  110.00  45.00 -90.00   58
120  \w     98.00 156.00   0.50    5.00    --  110.00  45.00 150.00  116
121  \w     93.00 168.00   0.50    5.00    --  110.00  61.00   0.00  150
122  \w     96.00 127.00   0.50    5.00    --  110.00  45.00 -90.00   62
123  \w     71.00 107.00   0.50    5.00    --  110.00 -94.00 -60.00   72
124  \w    101.00 172.00   0.50    5.00    --  110.00  77.00-150.00  142
125  \w    101.00 173.00   0.50    5.00    --  110.00  77.00  60.00  144
126  \w    137.00 163.00   0.50    5.00    --  110.00  45.00 -30.00   52
127  \w     93.00 178.00   0.50    5.00    --  110.00  61.00 150.00  170
128  \w     80.00 106.00   0.50    5.00    --  110.00 -94.00 -30.00   52
129  \w     39.00  65.00   0.50    5.00    --  110.00 -94.00 -30.00   52
130  \w    142.00 167.00   0.50    5.00    --  110.00  61.00-180.00   50
131  \w     41.00  74.00   0.50    5.00    --  110.00 -94.00-150.00   66
132  \w     77.00 102.00   0.50    5.00    --  110.00 -94.00-150.00   50
133  \w     83.00 108.00   0.50    5.00    --  110.00-111.00  60.00   50
134  \w     37.00  62.00   0.50    5.00    --  110.00-111.00  60.00   50
135  \w     99.00 147.00   0.50    5.00    --  110.00  61.00 -60.00   96
136  \w     83.00 108.00   0.50    5.00    --  110.00 -61.00  30.00   50
137  \w    132.00 171.00   0.50    5.00    --  110.00  61.00 120.00   78
138  \w     93.00 130.00   0.50    5.00    --  110.00  61.00-180.00   74
139  \w     96.00 122.00   0.50    5.00    --  110.00  45.00 -30.00   52
140  \w    100.00 126.00   0.50    5.00    --  110.00  45.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0366104000
_diffrn_orient_matrix_UB_12      -0.0805003000
_diffrn_orient_matrix_UB_13      0.0434494000
_diffrn_orient_matrix_UB_21      -0.1662866000
_diffrn_orient_matrix_UB_22      0.0355134000
_diffrn_orient_matrix_UB_23      -0.0023131000
_diffrn_orient_matrix_UB_31      -0.0329337000
_diffrn_orient_matrix_UB_32      -0.0857341000
_diffrn_orient_matrix_UB_33      -0.0354391000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            81167
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.662
_diffrn_reflns_theta_min         3.219
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.226
_exptl_absorpt_correction_T_max  0.698
_exptl_absorpt_correction_T_min  0.270
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
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    1.631
_exptl_crystal_description       plate
_exptl_crystal_F_000             1503
_exptl_crystal_size_max          0.082
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.035
_refine_diff_density_max         1.138
_refine_diff_density_min         -2.387
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         12861
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0523P)^2^+7.8951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1041
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11547
_reflns_number_total             12861
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03992g2.cif
_cod_data_source_block           mlb-fs1_009_auto
_cod_depositor_comments
'Adding full bibliography for 7714872--7714877.cif.'
_cod_original_cell_volume        3064.69(5)
_cod_original_formula_sum        'C52 H86 B1.95 Br0.05 F7.80 N2 O6 P4 Re2'
_cod_database_code               7714873
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H86 N2 B2 F8 P4 O6 Re2'
_chemical_oxdiff_usercomment     Pilatus
_shelx_estimated_absorpt_t_max   0.738
_shelx_estimated_absorpt_t_min   0.518
_reflns_odcompleteness_completeness 99.54
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
F2 \\sim F3 \\sim F5 \\sim F6 \\sim F7 \\sim Br1: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Uanis(F6) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
2. Others
 Fixed Sof: F1(0.95) B1(0.95) F2(0.48) F3(0.48) F4(0.48) F5(0.47) F6(0.47)
 F7(0.47) Br1(0.05)
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C27(H27A,H27B), C33(H33A,H33B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C29(H29), C30(H30), C31(H31)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C)
;
_shelx_res_checksum              39651
_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 4.109
_oxdiff_exptl_absorpt_empirical_full_min 0.296