Reduction of (pddi)Cr reveals redox noninnocence <i>via</i> C-C bond formation amidst competing electrophilicity: [(cpta)CrMe<sub><i>n</i></sub>]<sup>-</sup> (<i>n</i> = 0, 1) and [(pta)Cr]<sup/>.
D'Arpino, Alexander A; Wolczanski, Peter T.; MacMillan, Samantha N.; Cundari, Thomas R.; Krumov, Mihail R.; Chemical communications (Cambridge, England) 60 (2024) 6785–6788; doi:10.1039/d4cc01690d

data_7133138
_publ_section_title
;
 Reduction of (pddi)Cr reveals redox noninnocence <i>via</i> C-C bond
 formation amidst competing electrophilicity:
 [(cpta)CrMe<sub><i>n</i></sub>]<sup>-</sup> (<i>n</i> = 0, 1) and
 [(pta)Cr]<sup/>.
;
_journal_issue                   53
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6785
_journal_page_last               6788
_journal_paper_doi               10.1039/d4cc01690d
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C42 H53 Cr N4, C16 H32 Li O4, C4 H10 O'
_chemical_formula_sum            'C62 H95 Cr Li N4 O5'
_chemical_formula_weight         1035.35
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2022-06-28
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                97.6690(10)
_cell_angle_beta                 105.2700(10)
_cell_angle_gamma                108.7830(10)
_cell_formula_units_Z            2
_cell_length_a                   11.76990(10)
_cell_length_b                   16.1506(2)
_cell_length_c                   17.7227(2)
_cell_measurement_reflns_used    46501
_cell_measurement_temperature    101(1)
_cell_measurement_theta_max      77.9340
_cell_measurement_theta_min      2.6410
_cell_volume                     2987.77(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -98.00 -72.00   0.50    1.51    --  -48.30-135.00 -73.00   52
  2  \w    -92.00 -19.00   0.50    1.51    --  -48.30 135.00  -8.00  146
  3  \w   -115.00 -69.00   0.50    1.51    --  -48.30-134.00 105.00   92
  4  \w    -89.00 -64.00   0.50    1.51    --  -48.30 134.00 172.00   50
  5  \w     39.00  82.00   0.50    1.51    --   48.30-134.00 105.00   86
  6  \w     73.00  99.00   0.50    1.51    --   48.30-135.00 -73.00   52
  7  \w   -137.00-112.00   0.50    6.04    --  -86.25-134.00 105.00   50
  8  \w   -137.00-112.00   0.50    6.04    --  -86.25-135.00 -73.00   50
  9  \w    -80.00 -55.00   0.50    6.04    --  -86.25 134.00 172.00   50
 10  \w    -80.00 -55.00   0.50    6.04    --  -86.25 135.00  -8.00   50
 11  \w     94.00 134.00   0.50    6.04    --  107.75 135.00  -8.00   80
 12  \w     78.00 103.00   0.50    6.04    --  107.75-134.00 105.00   50
 13  \w     79.00 113.00   0.50    6.04    --  107.75-135.00 -73.00   68
 14  \w    133.00 158.00   0.50    6.04    --  107.75 134.00 172.00   50
 15  \w   -119.00 -74.00   0.50    1.51    --  -48.30-125.00-180.00   90
 16  \w   -116.00 -73.00   0.50    1.51    --  -48.30-125.00 -30.00   86
 17  \w    -42.00  24.00   0.50    1.51    --  -48.30  37.00-180.00  132
 18  \w    -42.00  24.00   0.50    1.51    --  -48.30  37.00-120.00  132
 19  \w    -15.00  24.00   0.50    1.51    --  -48.30  19.00 -30.00   78
 20  \w    -26.00  16.00   0.50    1.51    --  -48.30  19.00 120.00   84
 21  \w     56.00 114.00   0.50    1.51    --   48.30  77.00 -30.00  116
 22  \w    -48.00 -15.00   0.50    6.04    --  -86.25  45.00 -60.00   66
 23  \w     84.00 109.00   0.50    6.04    --  107.75-117.00  34.03   50
 24  \w     37.00  68.00   0.50    6.04    --  107.75 -77.00 -90.00   62
 25  \w     44.00  70.00   0.50    6.04    --  107.75-115.00   4.30   52
 26  \w     75.00 109.00   0.50    6.04    --  107.75-115.00   4.30   68
 27  \w     38.00 101.00   0.50    6.04    --  107.75 -77.00 -60.00  126
 28  \w     40.00  70.00   0.50    6.04    --  107.75-102.00  95.37   60
 29  \w     40.00  67.00   0.50    6.04    --  107.75 -61.00  90.00   54
 30  \w     61.00 102.00   0.50    6.04    --  107.75 -94.00 120.00   82
 31  \w     66.00  99.00   0.50    6.04    --  107.75 -94.00-180.00   66
 32  \w    103.00 170.00   0.50    6.04    --  107.75  45.00 -90.00  134
 33  \w     39.00  67.00   0.50    6.04    --  107.75 -61.00  60.00   56
 34  \w     57.00 108.00   0.50    6.04    --  107.75-109.00  61.18  102
 35  \w     89.00 177.00   0.50    6.04    --  107.75  77.00-180.00  176
 36  \w    106.00 132.00   0.50    6.04    --  107.75  45.00   0.00   52
 37  \w     76.00 102.00   0.50    6.04    --  107.75 -77.00 -90.00   52
 38  \w     56.00  96.00   0.50    6.04    --  107.75 -74.00-116.35   80
 39  \w     36.00  70.00   0.50    6.04    --  107.75 -61.00  30.00   68
 40  \w    110.00 178.00   0.50    6.04    --  107.75  45.00 120.00  136
 41  \w     44.00  76.00   0.50    6.04    --  107.75-101.00  41.93   64
 42  \w     38.00  63.00   0.50    6.04    --  107.75 -94.00 150.00   50
 43  \w     74.00 100.00   0.50    6.04    --  107.75 -94.00 150.00   52
 44  \w     37.00  62.00   0.50    6.04    --  107.75 -82.00  13.76   50
 45  \w     44.00  70.00   0.50    6.04    --  107.75 -61.00-180.00   52
 46  \w     41.00  69.00   0.50    6.04    --  107.75 -94.00-150.00   56
 47  \w     98.00 132.00   0.50    6.04    --  107.75-154.00  17.63   68
 48  \w     74.00 108.00   0.50    6.04    --  107.75-107.00-150.87   68
 49  \w     74.00 106.00   0.50    6.04    --  107.75-125.00  30.00   64
 50  \w     77.00 106.00   0.50    6.04    --  107.75 -94.00-150.00   58
 51  \w    127.00 173.00   0.50    6.04    --  107.75  45.00 -60.00   92
 52  \w     60.00 108.00   0.50    6.04    --  107.75-125.00 -30.00   96
 53  \w     36.00  86.00   0.50    6.04    --  107.75 -77.00  90.00  100
 54  \w     73.00 108.00   0.50    6.04    --  107.75-110.00 -76.37   70
 55  \w     90.00 170.00   0.50    6.04    --  107.75  74.00 160.57  160
 56  \w    118.00 144.00   0.50    6.04    --  107.75  55.00-138.49   52
 57  \w    130.00 156.00   0.50    6.04    --  107.75  61.00  90.00   52
 58  \w    140.00 177.00   0.50    6.04    --  107.75  15.00 150.00   74
 59  \w     39.00  96.00   0.50    6.04    --  107.75 -77.00-150.00  114
 60  \w     99.00 177.00   0.50    6.04    --  107.75  15.00  60.00  156
 61  \w     37.00  63.00   0.50    6.04    --  107.75-125.00  30.00   52
 62  \w     56.00  83.00   0.50    6.04    --  107.75-154.00  17.63   54
 63  \w     36.00  66.00   0.50    6.04    --  107.75 -77.00   0.00   60
 64  \w     99.00 138.00   0.50    6.04    --  107.75  61.00  60.00   78
 65  \w    120.00 148.00   0.50    6.04    --  107.75  68.00  74.10   56
 66  \w     47.00  73.00   0.50    6.04    --  107.75 -77.00 150.00   52
 67  \w     39.00  69.00   0.50    6.04    --  107.75 -94.00   0.00   60
 68  \w     51.00  77.00   0.50    6.04    --  107.75 -94.00  90.00   52
 69  \w    100.00 135.00   0.50    6.04    --  107.75  41.00 142.44   70
 70  \w     36.00  70.00   0.50    6.04    --  107.75 -61.00-150.00   68
 71  \w     64.00  90.00   0.50    6.04    --  107.75 -94.00 -90.00   52
 72  \w     40.00  65.00   0.50    6.04    --  107.75 -77.00 139.42   50
 73  \w     81.00 106.00   0.50    6.04    --  107.75 -77.00 139.42   50
 74  \w     36.00  65.00   0.50    6.04    --  107.75-107.00 141.15   58
 75  \w     76.00 107.00   0.50    6.04    --  107.75-107.00 141.15   62
 76  \w     69.00 106.00   0.50    6.04    --  107.75-125.00  60.00   74
 77  \w     94.00 122.00   0.50    6.04    --  107.75 -82.00  13.76   56
 78  \w     76.00 107.00   0.50    6.04    --  107.75-102.00  95.37   62
 79  \w    141.00 174.00   0.50    6.04    --  107.75  41.00 142.44   66
 80  \w    127.00 153.00   0.50    6.04    --  107.75  45.00-150.00   52
 81  \w    109.00 174.00   0.50    6.04    --  107.75  45.00-120.00  130
 82  \w     97.00 145.00   0.50    6.04    --  107.75  30.00 -30.00   96
 83  \w     99.00 135.00   0.50    6.04    --  107.75  15.00-150.00   72
 84  \w    147.00 172.00   0.50    6.04    --  107.75  15.00-150.00   50
 85  \w     88.00 125.00   0.50    6.04    --  107.75  77.00 -60.00   74
 86  \w     57.00  83.00   0.50    6.04    --  107.75 -77.00 -30.00   52
 87  \w     50.00  76.00   0.50    6.04    --  107.75 -77.00  30.00   52
 88  \w    123.00 149.00   0.50    6.04    --  107.75 101.00 -44.01   52
 89  \w     84.00 110.00   0.50    6.04    --  107.75-125.00-180.00   52
 90  \w     68.00 108.00   0.50    6.04    --  107.75-125.00-150.00   80
 91  \w     44.00  71.00   0.50    6.04    --  107.75-107.00-150.87   54
 92  \w     85.00 120.00   0.50    6.04    --  107.75-136.00 115.95   70
 93  \w     98.00 124.00   0.50    6.04    --  107.75  45.00-180.00   52
 94  \w    109.00 144.00   0.50    6.04    --  107.75  30.00 -60.00   70
 95  \w    108.00 133.00   0.50    6.04    --  107.75  30.00  30.00   50
 96  \w    125.00 151.00   0.50    6.04    --  107.75 125.00-180.00   52
 97  \w    153.00 178.00   0.50    6.04    --  107.75 125.00 -90.00   50
 98  \w    121.00 147.00   0.50    6.04    --  107.75 125.00  30.00   52
 99  \w     98.00 150.00   0.50    6.04    --  107.75  30.00-180.00  104
100  \w     93.00 123.00   0.50    6.04    --  107.75  61.00  90.00   60
101  \w     36.00  71.00   0.50    6.04    --  107.75 -61.00-120.00   70
102  \w     74.00  99.00   0.50    6.04    --  107.75  -2.00-115.46   50
103  \w     41.00  66.00   0.50    6.04    --  107.75 -61.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0581425000
_diffrn_orient_matrix_UB_12      -0.0845280000
_diffrn_orient_matrix_UB_13      -0.0700982000
_diffrn_orient_matrix_UB_21      0.0047950000
_diffrn_orient_matrix_UB_22      -0.0596711000
_diffrn_orient_matrix_UB_23      0.0608031000
_diffrn_orient_matrix_UB_31      -0.1341296000
_diffrn_orient_matrix_UB_32      -0.0077568000
_diffrn_orient_matrix_UB_33      -0.0004784000
_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  0.0485
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            80638
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.219
_diffrn_reflns_theta_min         2.662
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.952
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.582
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
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            'clear green'
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       needle
_exptl_crystal_F_000             1124
_exptl_crystal_size_max          0.419
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.068
_refine_diff_density_max         0.928
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     681
_refine_ls_number_reflns         12726
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0758P)^2^+1.2768P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1275
_refine_ls_wR_factor_ref         0.1288
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12150
_reflns_number_total             12726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01690d2.cif
_cod_data_source_block           raad7_abs
_cod_depositor_comments
'Adding full bibliography for 7133137--7133141.cif.'
_cod_original_cell_volume        2987.76(6)
_cod_database_code               7133138
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C62H95CrLiN4O5
_chemical_oxdiff_usercomment     'Crystallized from THF/ether.'
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.495
_reflns_odcompleteness_completeness 98.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.89
_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. Others
 Sof(H44C)=Sof(H44D)=Sof(C45B)=Sof(H45C)=Sof(H45D)=1-FVAR(1)
 Sof(H44A)=Sof(H44B)=Sof(C45A)=Sof(H45A)=Sof(H45B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C19(H19), C20(H20), C36(H36), C39(H39)
3.b Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C43(H43A,H43B), C44(H44C,H44D), C44(H44A,H44B), C45A(H45A,
 H45B), C45B(H45C,H45D), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B),
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
  C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C2S(H2SA,
 H2SB), C3S(H3SA,H3SB)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16), C17(H17), C25(H25),
 C26(H26), C27(H27), C28(H28), C32(H32), C33(H33), C34(H34)
3.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C015(H01A,H01B,H01C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C1S(H1SA,
 H1SB,H1SC), C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              75642
_shelx_hkl_checksum              81964
_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 1.337
_oxdiff_exptl_absorpt_empirical_full_min 0.651