Ex situ generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation step between two oxidative addition Pd-complexes
Skrydstrup, Troels; Kristensen, Steffan Kvist; Eikeland, Espen; Taarning, Esben; Lindhardt, Anders T.; Chem. Sci.  (2017) –; doi:10.1039/C7SC03912C

data_1547635
_publ_section_title
;
 Ex situ generation of stoichiometric HCN and its application in the
 Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation
 step between two oxidative addition Pd-complexes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03912C
_journal_year                    2017
_chemical_formula_moiety         'C25 H54 N P2 Pd'
_chemical_formula_sum            'C25 H54 N P2 Pd'
_chemical_formula_weight         537.03
_chemical_properties_physical    ', Air-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'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.

Sheldrick, G.M. (2015). Acta Cryst. C71, 3-8.
;
_audit_update_record
;
2016-09-19 deposited with the CCDC.
2017-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90.2601(18)
_cell_angle_beta                 90.0672(18)
_cell_angle_gamma                90.8113(19)
_cell_formula_units_Z            8
_cell_length_a                   12.6035(3)
_cell_length_b                   17.2591(4)
_cell_length_c                   25.6455(5)
_cell_measurement_reflns_used    18942
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      28.2410
_cell_measurement_theta_min      1.7840
_cell_volume                     5577.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_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    -20.00  69.00   1.00   90.00    --   18.69 -99.00 -30.00   89
  2  \w    -20.00  69.00   1.00   90.00    --   18.69 -99.00 120.00   89
  3  \w    -73.00  60.00   1.00   90.00    --   18.69 -57.00 -60.00  133
  4  \w    -73.00  60.00   1.00   90.00    --   18.69 -57.00-150.00  133
  5  \w    -23.00  45.00   1.00   90.00    --   18.69  57.00-120.00   68
  6  \w     35.00  76.00   1.00   90.00    --  -19.62 178.00  90.00   41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0370517000
_diffrn_orient_matrix_UB_12      0.0274919000
_diffrn_orient_matrix_UB_13      0.0090926000
_diffrn_orient_matrix_UB_21      -0.0316792000
_diffrn_orient_matrix_UB_22      -0.0303913000
_diffrn_orient_matrix_UB_23      0.0105322000
_diffrn_orient_matrix_UB_31      0.0281331000
_diffrn_orient_matrix_UB_32      0.0031499000
_diffrn_orient_matrix_UB_33      0.0239034000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            58488
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.588
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.792
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79037
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2296
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.874
_refine_diff_density_min         -0.978
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1093
_refine_ls_number_reflns         22646
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0601
_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^)+(0.0314P)^2^+22.0524P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1272
_refine_ls_wR_factor_ref         0.1373
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16991
_reflns_number_total             22646
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03912c2.cif
_cod_data_source_block           33
_cod_database_code               1547635
_chemical_oxdiff_formula         PdP2NC20H20
_reflns_odcompleteness_completeness 99.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N02U-C00E = N00S-C00D = N01U-C00I = N02W-C00G
 1.14 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(Pd04) = Uanis(Pd)
Uanis(Pd01) = Uanis(Pd1)
Uanis(Pd02) = Uanis(Pd2)
Uanis(Pd03) = Uanis(Pd3)
4. Others
 Sof(Pd)=1-FVAR(1)
 Sof(Pd04)=FVAR(1)
 Sof(Pd1)=1-FVAR(2)
 Sof(Pd01)=FVAR(2)
 Sof(Pd2)=1-FVAR(3)
 Sof(Pd02)=FVAR(3)
 Sof(Pd3)=1-FVAR(4)
 Sof(Pd03)=FVAR(4)
5.a Idealised Me refined as rotating group:
 C00K(H00G,H00H,H00I), C00P(H00S,H00T,H00U), C00Q(H00J,H00K,H00L), C00U(H00A,
 H00B,H00C), C00V(H00M,H00N,H00O), C00W(H00D,H00E,H00F), C00Z(H00P,H00Q,H00R),
 C014(H01J,H01K,H01L), C016(H01M,H01N,H01O), C017(H2CA,H,HA), C018(H5AA,HB,HC),
 C01D(H01P,H01Q,H01R), C01E(H01S,H01T,H01U), C01F(H6AA,HD,HE), C01G(H3CA,HF,HG),
  C01H(H01A,H01B,H01C), C01I(H01D,H01E,H01F), C01J(H7AA,HH,HI), C01K(H8AA,HJ,
 HK), C01L(H4CA,HL,HM), C01M(H9AA,HN,HO), C01N(H0BA,HP,HQ), C01O(H5CA,HR,HS),
 C01P(H01V,H01W,H01X), C01Q(H01Y,HT,HU), C01R(H01Z,HV,HW), C01S(H01,HX,HY),
 C01T(H6CA,HZ,H4DA), C01W(H1BA,H5DA,H6DA), C01X(H01G,H01H,H01I), C01Z(H2BA,H7DA,
 H8DA), C020(H3BA,H9DA,H0EA), C023(H02A,H02B,H02C), C024(H4BA,H1EA,H2EA),
 C025(H02D,H02E,H02F), C026(H0AA,H3EA,H4EA), C027(H5BA,H5EA,H6EA), C028(H02G,
 H02H,H02I), C029(H6BA,H7EA,H8EA), C02A(H7CA,H9EA,H0FA), C02B(H1AA,H1FA,H2FA),
 C02C(H8CA,H3FA,H4FA), C02D(H02J,H02K,H02L), C02E(H2AA,H5FA,H6FA), C02F(H7BA,
 H7FA,H8FA), C02G(H8BA,H9FA,H0GA), C02H(H9CA,H1GA,H2GA), C02I(H02M,H02N,H02O),
 C02J(H9BA,H3GA,H4GA), C02K(H0CA,H5GA,H6GA), C02L(H1CA,H7GA,H8GA), C02M(H02P,
 H02Q,H02R), C02N(H0DA,H9GA,H0HA), C02O(H02S,H02T,H02U), C02P(H02V,H02W,H02X),
 C02Q(H1DA,H1HA,H2HA), C02R(H2DA,H3HA,H4HA), C02S(H02Y,H5HA,H6HA), C02T(H3AA,
 H7HA,H8HA), C02V(H02Z,H9HA,H0IA), C02X(H3DA,H1IA,H2IA), C02Y(H4AA,H3IA,H4IA),
 C02Z(H02,H5IA,H6IA), C030(H03M,H03N,H03O), C031(H03J,H03K,H03L), C032(H03G,
 H03H,H03I), C033(H03A,H03B,H03C), C034(H03P,H03Q,H03R), C035(H03D,H03E,H03F),
 C036(H03S,H03T,H03U), C037(H03V,H03W,H03X), C038(H03Y,H7IA,H8IA)
;
_shelx_shelxl_version_number     2014/7
_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 1.445
_oxdiff_exptl_absorpt_empirical_full_min 0.756