Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations interconverting gyroscope and parachute like adducts
Zhu, Yun; Ehnbom, Andreas; Fiedler, Tobias; Shu, Yi; Bhuvanesh, Nattamai; Hall, Michael B.; Gladysz, John A.; Dalton Transactions  (2021) –; doi:10.1039/D1DT02321G

data_7708170
_publ_section_title
;
 Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines
 P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations
 interconverting gyroscope and parachute like adducts
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02321G
_journal_year                    2021
_chemical_formula_moiety         'C44 H89 Cl P2 Pt'
_chemical_formula_sum            'C44 H89 Cl P2 Pt'
_chemical_formula_weight         910.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-06-16
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2021-08-20 deposited with the CCDC.	2021-08-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.995(2)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   38.540(7)
_cell_length_b                   14.255(3)
_cell_length_c                   25.681(4)
_cell_measurement_reflns_used    9598
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      25.36
_cell_measurement_theta_min      2.21
_cell_volume                     14100(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX-II (BRUKER-NONIUS, 2003)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'APEX II'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0930
_diffrn_reflns_av_unetI/netI     0.0733
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            154056
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         1.655
_exptl_absorpt_coefficient_mu    3.137
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.4356
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1132 before and 0.0722 after correction.
The Ratio of minimum to maximum transmission is 0.5841.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             5736
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.927
_refine_diff_density_min         -1.925
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1676
_refine_ls_number_reflns         32379
_refine_ls_number_restraints     1956
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0934
_refine_ls_R_factor_gt           0.0585
_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^)+(0.0203P)^2^+104.3808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23095
_reflns_number_total             32379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02321g3.cif
_cod_data_source_block           new
_cod_database_code               7708170
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.744
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C91-C92 = C92-C93 = C93-C94 = C94-C95 = C95-C96 = C96-C97 = C97-C98 = C98-C99
 = C99-C100 = C100-C101 = C101-C102 = C102-C103 = C103-C104
 1.54 with sigma of 0.01
 C105-C106 = C106-C107 = C107-C108 = C108-C109 = C109-C110 = C110-C111 = C111-
 C112 = C112-C113 = C113-C114 = C114-C115 = C115-C116 = C116-C117 = C117-C118
 1.54 with sigma of 0.01
 C119-C120 = C120-C121 = C121-C122 = C122-C123 = C123-C124 = C124-C125 = C125-
 C126 = C126-C127 = C127-C128 = C128-C129 = C129-C130 = C130-C131 = C131-C132
 1.54 with sigma of 0.01
 C91-C93 = C93-C95 = C95-C97 = C97-C99 = C99-C101 = C101-C103 = C92-C94 = C94-
 C96 = C96-C98 = C98-C100 = C100-C102 = C102-C104
 2.5 with sigma of 0.01
 C105-C107 = C107-C109 = C109-C111 = C111-C113 = C113-C115 = C115-C117 = C106-
 C108 = C108-C110 = C110-C112 = C112-C114 = C114-C116 = C116-C118
 2.5 with sigma of 0.01
 C119-C121 = C121-C123 = C123-C125 = C125-C127 = C127-C129 = C129-C131 = C120-
 C122 = C122-C124 = C124-C126 = C126-C128 = C128-C130 = C130-C132
 2.5 with sigma of 0.01
3. Rigid bond restraints
 C91, C92, C93, C94, C95, C96, C97, C98, C99, C100, C101, C102, C103, C104,
 C105, C106, C107, C108, C109, C110, C111, C112, C113, C114, C115, C116, C117,
 C118, C119, C120, C121, C122, C123, C124, C125, C126, C127, C128, C129, C130,
 C131, C132, C291, C292, C293, C294, C295, C296, C297, C298, C299, C300, C301,
 C302, C303, C304, C305, C306, C307, C308, C309, C310, C311, C312, C313, C314,
 C315, C316, C317, C318, C319, C320, C321, C322, C323, C324, C325, C326, C327,
 C328, C329, C330, C331, C332
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim
C85 \\sim C86 \\sim C87 \\sim C88: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97 \\sim C98 \\sim
C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim
C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim
C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118 \\sim C119 \\sim
C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim
C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim C291 \\sim
C292 \\sim C293 \\sim C294 \\sim C295 \\sim C296 \\sim C297 \\sim C298 \\sim
C299 \\sim C300 \\sim C301 \\sim C302 \\sim C303 \\sim C304 \\sim C305 \\sim
C306 \\sim C307 \\sim C308 \\sim C309 \\sim C310 \\sim C311 \\sim C312 \\sim
C313 \\sim C314 \\sim C315 \\sim C316 \\sim C317 \\sim C318 \\sim C319 \\sim
C320 \\sim C321 \\sim C322 \\sim C323 \\sim C324 \\sim C325 \\sim C326 \\sim
C327 \\sim C328 \\sim C329 \\sim C330 \\sim C331 \\sim C332: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
5. Same fragment restrains
{C91, C92, C93, C94, C95, C96, C97, C98, C99, C100, C101, C102, C103, C104,
C105, C106, C107, C108, C109, C110, C111, C112, C113, C114, C115, C116, C117,
C118, C119, C120, C121, C122, C123, C124, C125, C126, C127, C128, C129, C130,
C131, C132} sigma for 1-2: 0.005, 1-3: 0.04
as
{C291, C292, C293, C294, C295, C296, C297, C298, C299, C300, C301, C302, C303,
C304, C305, C306, C307, C308, C309, C310, C311, C312, C313, C314, C315, C316,
C317, C318, C319, C320, C321, C322, C323, C324, C325, C326, C327, C328, C329,
C330, C331, C332}
6. Others
 Sof(C291)=Sof(H29A)=Sof(H29B)=Sof(C292)=Sof(H29C)=Sof(H29D)=Sof(C293)=
 Sof(H29E)=Sof(H29F)=Sof(C294)=Sof(H29G)=Sof(H29H)=Sof(C295)=Sof(H29I)=
 Sof(H29J)=Sof(C296)=Sof(H29K)=Sof(H29L)=Sof(C297)=Sof(H29M)=Sof(H29N)=
 Sof(C298)=Sof(H29O)=Sof(H29P)=Sof(C299)=Sof(H29Q)=Sof(H29R)=Sof(C300)=
 Sof(H30A)=Sof(H30B)=Sof(C301)=Sof(H30C)=Sof(H30D)=Sof(C302)=Sof(H30E)=
 Sof(H30F)=Sof(C303)=Sof(H30G)=Sof(H30H)=Sof(C304)=Sof(H30I)=Sof(H30J)=
 Sof(C305)=Sof(H30K)=Sof(H30L)=Sof(C306)=Sof(H30M)=Sof(H30N)=Sof(C307)=
 Sof(H30O)=Sof(H30P)=Sof(C308)=Sof(H30Q)=Sof(H30R)=Sof(C309)=Sof(H30S)=
 Sof(H30T)=Sof(C310)=Sof(H31A)=Sof(H31B)=Sof(C311)=Sof(H31C)=Sof(H31D)=
 Sof(C312)=Sof(H31E)=Sof(H31F)=Sof(C313)=Sof(H31G)=Sof(H31H)=Sof(C314)=
 Sof(H31I)=Sof(H31J)=Sof(C315)=Sof(H31K)=Sof(H31L)=Sof(C316)=Sof(H31M)=
 Sof(H31N)=Sof(C317)=Sof(H31O)=Sof(H31P)=Sof(C318)=Sof(H31Q)=Sof(H31R)=
 Sof(C319)=Sof(H31S)=Sof(H31T)=Sof(C320)=Sof(H32A)=Sof(H32B)=Sof(C321)=
 Sof(H32C)=Sof(H32D)=Sof(C322)=Sof(H32E)=Sof(H32F)=Sof(C323)=Sof(H32G)=
 Sof(H32H)=Sof(C324)=Sof(H32I)=Sof(H32J)=Sof(C325)=Sof(H32K)=Sof(H32L)=
 Sof(C326)=Sof(H32M)=Sof(H32N)=Sof(C327)=Sof(H32O)=Sof(H32P)=Sof(C328)=
 Sof(H32Q)=Sof(H32R)=Sof(C329)=Sof(H32S)=Sof(H32T)=Sof(C330)=Sof(H33A)=
 Sof(H33B)=Sof(C331)=Sof(H33C)=Sof(H33D)=Sof(C332)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C93)=Sof(H93A)=
 Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C96)=
 Sof(H96A)=Sof(H96B)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(C98)=Sof(H98A)=Sof(H98B)=
 Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(C101)=Sof(H10C)=
 Sof(H10D)=Sof(C102)=Sof(H10E)=Sof(H10F)=Sof(C103)=Sof(H10G)=Sof(H10H)=
 Sof(C104)=Sof(H10I)=Sof(H10J)=Sof(C105)=Sof(H10K)=Sof(H10L)=Sof(C106)=
 Sof(H10M)=Sof(H10N)=Sof(C107)=Sof(H10O)=Sof(H10P)=Sof(C108)=Sof(H10Q)=
 Sof(H10R)=Sof(C109)=Sof(H10S)=Sof(H10T)=Sof(C110)=Sof(H11A)=Sof(H11B)=
 Sof(C111)=Sof(H11C)=Sof(H11D)=Sof(C112)=Sof(H11E)=Sof(H11F)=Sof(C113)=
 Sof(H11G)=Sof(H11H)=Sof(C114)=Sof(H11I)=Sof(H11J)=Sof(C115)=Sof(H11K)=
 Sof(H11L)=Sof(C116)=Sof(H11M)=Sof(H11N)=Sof(C117)=Sof(H11O)=Sof(H11P)=
 Sof(C118)=Sof(H11Q)=Sof(H11R)=Sof(C119)=Sof(H11S)=Sof(H11T)=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)=Sof(C131)=Sof(H13C)=Sof(H13D)=
 Sof(C132)=Sof(H13E)=Sof(H13F)=FVAR(1)
7.a Riding coordinates:
 C2(H2A,H2B,H2C), C46(H46A,H46B,H46C), C132(H13E,H13F)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), C9(H9A,H9B), C10(H10U,H10V), C11(H11U,H11V), C12(H12U,H12V),
 C13(H13G,H13H), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B),
  C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,
 H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
 C27(H27A,H27B), C28(H28A,H28B), C29(H29S,H29T), C30(H30U,H30V), C31(H31U,H31V),
  C32(H32U,H32V), C33(H33G,H33H), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,
 H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B),
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B),
  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), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B),
  C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
  C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,
 H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B),
  C89(H89A,H89B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,
 H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B),
 C99(H99A,H99B), C100(H10A,H10B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,
 H10H), C104(H10I,H10J), C105(H10K,H10L), C106(H10M,H10N), C107(H10O,H10P),
 C108(H10Q,H10R), C109(H10S,H10T), C110(H11A,H11B), C111(H11C,H11D), C112(H11E,
 H11F), C113(H11G,H11H), C114(H11I,H11J), C115(H11K,H11L), C116(H11M,H11N),
 C117(H11O,H11P), C118(H11Q,H11R), C119(H11S,H11T), 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), C131(H13C,H13D), C291(H29A,H29B), C292(H29C,H29D), C293(H29E,H29F),
 C294(H29G,H29H), C295(H29I,H29J), C296(H29K,H29L), C297(H29M,H29N), C298(H29O,
 H29P), C299(H29Q,H29R), C300(H30A,H30B), C301(H30C,H30D), C302(H30E,H30F),
 C303(H30G,H30H), C304(H30I,H30J), C305(H30K,H30L), C306(H30M,H30N), C307(H30O,
 H30P), C308(H30Q,H30R), C309(H30S,H30T), C310(H31A,H31B), C311(H31C,H31D),
 C312(H31E,H31F), C313(H31G,H31H), C314(H31I,H31J), C315(H31K,H31L), C316(H31M,
 H31N), C317(H31O,H31P), C318(H31Q,H31R), C319(H31S,H31T), C320(H32A,H32B),
 C321(H32C,H32D), C322(H32E,H32F), C323(H32G,H32H), C324(H32I,H32J), C325(H32K,
 H32L), C326(H32M,H32N), C327(H32O,H32P), C328(H32Q,H32R), C329(H32S,H32T),
 C330(H33A,H33B), C331(H33C,H33D), C332(H33E,H33F)
7.c Me refined with riding coordinates:
 C90(H90A,H90B,H90C)
;
_shelx_res_checksum              53784
_olex2_submission_special_instructions 'No special instructions were received'