data_1100791 _publ_requested_journal 'Organometallics' _publ_section_title ; Cyanamido-Bridged Diiridium Complex: a Reactive Building Block for Polynuclear Cyanamido Complexes ; loop_ _publ_author_name 'Hidenobu Kajitani' 'Yoshiaki Tanabe' 'Shigeki Kuwata' 'Masakazu Iwasaki' _publ_section_synopsis ; [Cp*IrCl2]2 reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(\m2-NCN-N,N)]2 (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)2(ML)(\m3-NCN-N,N,N)2]+ (ML = Rh(cod), CpRu, Pd(\m3-C3H5)) in reactions with cationic group 8-10 metal complexes such as [Rh(cod)(acetone)n]+, [CpRu(MeCN)3]+, and [Pd(\m3-C3H5)(acetone)n]+, while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(\m3-NCN-N,N,N)]4. ; _publ_section_abstract ; [Cp*IrCl2]2 reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(\m2-NCN-N,N)]2 (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)2(ML)(\m3-NCN-N,N,N)2]+ (ML = Rh(cod), CpRu, Pd(\m3-C3H5)) in reactions with cationic group 8-10 metal complexes such as [Rh(cod)(acetone)n]+, [CpRu(MeCN)3]+, and [Pd(\m3-C3H5)(acetone)n]+, while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(\m3-NCN-N,N,N)]4. ; _publ_section_exptl_prep ; Reaction of 1 and 2 equiv Na2NCN at room temperature affords 5. 4 reacts with CO, PMe3, dppm, and [Cp*Rh(acetone)n]+ to afford 6.8d, 9, and 10a, respectively. ; _publ_section_exptl_refinement ; Crystals of 5, 6, 8d, 9, and 10a are obtained by recrystallization from CH2Cl2-ether, toluene-hexane, benzene-hexane, benzene-hexane, and CH2Cl2-methanol, respectively. ; _chemical_formula_sum 'C56 H61 Ir2 N4 P2 ' _chemical_formula_moiety 'C56 H61 Ir2 N4 P2 ' _chemical_formula_weight 1236.51 _chemical_melting_point ? _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 '+X,+Y,+Z' 2 '-X,-Y,-Z' _cell_length_a 12.084(4) _cell_length_b 12.105(4) _cell_length_c 19.525(7) _cell_angle_alpha 99.37(1) _cell_angle_beta 91.82(1) _cell_angle_gamma 118.88(1) _cell_volume 2447(1) _cell_formula_units_Z 2 _cell_measurement_reflns_used 20891 _cell_measurement_theta_min 1.9 _cell_measurement_theta_max 27.5 _cell_measurement_temperature 294.1 _exptl_crystal_description 'block' _exptl_crystal_colour 'dark' _exptl_crystal_size_max 0.70 _exptl_crystal_size_mid 0.70 _exptl_crystal_size_min 0.40 _exptl_crystal_density_diffrn 1.678 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1218.00 _exptl_absorpt_coefficient_mu 5.555 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.040 _exptl_absorpt_correction_T_max 0.108 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 24110 _diffrn_reflns_av_R_equivalents 0.033 _diffrn_reflns_theta_max 27.46 _diffrn_measured_fraction_theta_max 0.9851 _diffrn_reflns_theta_full 27.46 _diffrn_measured_fraction_theta_full 0.9851 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 25 _reflns_number_total 10868 _reflns_number_gt 8788 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0310 _refine_ls_wR_factor_ref 0.0360 _refine_ls_hydrogen_treatment refall _refine_ls_number_reflns 8788 _refine_ls_number_parameters 638 _refine_ls_goodness_of_fit_ref 1.005 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[1.8500\s(Fo^2^) + 0.5000]' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 1.71 #(0.155, 0.548, 0.280) _refine_diff_density_min -1.67 _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; 'H' 'H' 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; 'N' 'N' 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; 'P' 'P' 0.102 0.094 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; 'Ir' 'Ir' -1.444 7.990 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ir(1) Ir 0.10772(1) 0.47498(1) 0.27106(1) 0.02367(5) Uani 1.00 1 d . . . Ir(2) Ir 0.40851(1) 0.70784(1) 0.33470(1) 0.02686(5) Uani 1.00 1 d . . . P(1) P 0.1919(1) 0.3908(1) 0.19052(5) 0.0254(3) Uani 1.00 1 d . . . P(2) P 0.4710(1) 0.6056(1) 0.25112(6) 0.0280(3) Uani 1.00 1 d . . . N(1) N 0.2496(3) 0.6599(4) 0.2662(2) 0.030(1) Uani 1.00 1 d . . . N(2) N 0.2553(6) 0.7590(5) 0.1646(3) 0.060(2) Uani 1.00 1 d . . . N(3) N 0.2708(4) 0.5171(4) 0.3376(2) 0.031(1) Uani 1.00 1 d . . . N(4) N 0.2490(5) 0.4371(5) 0.4468(3) 0.066(2) Uani 1.00 1 d . . . C(1) C 0.2524(5) 0.7100(4) 0.2125(3) 0.035(1) Uani 1.00 1 d . . . C(2) C 0.2588(5) 0.4762(5) 0.3951(3) 0.038(1) Uani 1.00 1 d . . . C(3) C -0.0940(4) 0.3236(5) 0.2482(3) 0.040(1) Uani 1.00 1 d . . . C(4) C -0.0569(4) 0.3560(5) 0.3221(3) 0.040(1) Uani 1.00 1 d . . . C(5) C -0.0246(5) 0.4878(5) 0.3453(3) 0.041(1) Uani 1.00 1 d . . . C(6) C -0.0396(5) 0.5354(5) 0.2871(3) 0.040(1) Uani 1.00 1 d . . . C(7) C -0.0782(5) 0.4362(5) 0.2264(3) 0.041(1) Uani 1.00 1 d . . . C(8) C -0.1504(6) 0.1918(6) 0.2041(4) 0.073(2) Uani 1.00 1 d . . . C(9) C -0.0648(7) 0.2695(7) 0.3708(4) 0.066(2) Uani 1.00 1 d . . . C(10) C 0.0071(6) 0.5578(7) 0.4193(3) 0.068(2) Uani 1.00 1 d . . . C(11) C -0.0191(7) 0.6675(7) 0.2884(4) 0.075(3) Uani 1.00 1 d . . . C(12) C -0.1168(6) 0.4477(8) 0.1551(3) 0.074(2) Uani 1.00 1 d . . . C(13) C 0.5956(5) 0.8672(5) 0.3851(3) 0.042(1) Uani 1.00 1 d . . . C(14) C 0.5305(5) 0.7998(5) 0.4373(3) 0.044(1) Uani 1.00 1 d . . . C(15) C 0.4205(5) 0.8167(5) 0.4435(3) 0.046(1) Uani 1.00 1 d . . . C(16) C 0.4170(5) 0.8869(5) 0.3946(3) 0.049(2) Uani 1.00 1 d . . . C(17) C 0.5240(5) 0.9166(5) 0.3554(3) 0.042(1) Uani 1.00 1 d . . . C(18) C 0.7266(5) 0.8932(6) 0.3699(4) 0.063(2) Uani 1.00 1 d . . . C(19) C 0.5758(7) 0.7437(7) 0.4865(3) 0.072(2) Uani 1.00 1 d . . . C(20) C 0.3322(7) 0.7696(6) 0.4977(3) 0.073(2) Uani 1.00 1 d . . . C(21) C 0.3187(7) 0.9263(6) 0.3831(4) 0.080(3) Uani 1.00 1 d . . . C(22) C 0.5627(7) 1.0021(5) 0.3034(3) 0.067(2) Uani 1.00 1 d . . . C(23) C 0.1070(4) 0.3336(5) 0.1013(2) 0.032(1) Uani 1.00 1 d . . . C(24) C 0.0314(5) 0.2041(5) 0.0717(3) 0.049(1) Uani 1.00 1 d . . . C(25) C -0.0349(6) 0.1652(7) 0.0060(3) 0.070(2) Uani 1.00 1 d . . . C(26) C -0.0301(7) 0.2510(8) -0.0317(3) 0.071(2) Uani 1.00 1 d . . . C(27) C 0.0458(6) 0.3818(7) -0.0036(3) 0.059(2) Uani 1.00 1 d . . . C(28) C 0.1122(5) 0.4228(6) 0.0634(3) 0.045(2) Uani 1.00 1 d . . . C(29) C 0.2070(5) 0.2537(4) 0.2046(2) 0.033(1) Uani 1.00 1 d . . . C(30) C 0.1744(7) 0.2061(6) 0.2639(3) 0.059(2) Uani 1.00 1 d . . . C(31) C 0.1802(9) 0.0973(7) 0.2721(4) 0.090(3) Uani 1.00 1 d . . . C(32) C 0.2211(8) 0.0379(7) 0.2213(4) 0.081(3) Uani 1.00 1 d . . . C(33) C 0.2558(6) 0.0855(6) 0.1623(4) 0.059(2) Uani 1.00 1 d . . . C(34) C 0.2509(5) 0.1944(5) 0.1548(3) 0.047(2) Uani 1.00 1 d . . . C(35) C 0.3514(4) 0.5069(4) 0.1751(2) 0.029(1) Uani 1.00 1 d . . . C(36) C 0.5263(4) 0.5015(4) 0.2788(3) 0.034(1) Uani 1.00 1 d . . . C(37) C 0.5549(6) 0.5126(5) 0.3489(3) 0.046(2) Uani 1.00 1 d . . . C(38) C 0.6101(6) 0.4472(6) 0.3724(3) 0.057(2) Uani 1.00 1 d . . . C(39) C 0.6347(6) 0.3667(6) 0.3251(4) 0.060(2) Uani 1.00 1 d . . . C(40) C 0.6029(6) 0.3514(6) 0.2551(4) 0.059(2) Uani 1.00 1 d . . . C(41) C 0.5500(5) 0.4202(6) 0.2311(3) 0.049(2) Uani 1.00 1 d . . . C(42) C 0.6015(4) 0.7104(5) 0.2063(2) 0.035(1) Uani 1.00 1 d . . . C(43) C 0.7201(5) 0.7188(5) 0.2129(3) 0.052(2) Uani 1.00 1 d . . . C(44) C 0.8165(5) 0.8014(6) 0.1793(4) 0.064(2) Uani 1.00 1 d . . . C(45) C 0.7952(6) 0.8750(6) 0.1411(4) 0.069(2) Uani 1.00 1 d . . . C(46) C 0.6798(6) 0.8688(5) 0.1341(3) 0.055(2) Uani 1.00 1 d . . . C(47) C 0.5828(5) 0.7873(4) 0.1679(3) 0.042(1) Uani 1.00 1 d . . . C(48) C 0.592(1) 0.474(1) 0.0217(4) 0.101(4) Uani 1.00 1 d . . . C(49) C 0.6249(9) 0.594(1) 0.0125(5) 0.102(4) Uani 1.00 1 d . . . C(50) C 0.530(1) 0.618(1) -0.0110(5) 0.111(4) Uani 1.00 1 d . . . C(51) C 0.0366(8) -0.0409(8) 0.4405(4) 0.081(3) Uani 1.00 1 d . . . C(52) C 0.0715(6) 0.0873(7) 0.4602(4) 0.066(2) Uani 1.00 1 d . . . C(53) C 0.0360(8) 0.1267(7) 0.5194(4) 0.076(3) Uani 1.00 1 d . . . C(54) C 0.569(2) 1.106(2) 0.050(1) 0.165(7) Uani 1.00 1 d . . . C(55) C 0.478(3) 0.994(3) 0.0650(8) 0.156(8) Uani 1.00 1 d . . . C(56) C 0.413(1) 0.893(2) 0.015(2) 0.150(6) Uani 1.00 1 d . . . H(1) H -0.2355 0.1639 0.1861 0.070 Uiso 1.00 1 c R . . H(2) H -0.1020 0.1932 0.1666 0.070 Uiso 1.00 1 c R . . H(3) H -0.1498 0.1342 0.2316 0.070 Uiso 1.00 1 c R . . H(4) H -0.1263 0.2625 0.4015 0.083 Uiso 1.00 1 c R . . H(5) H -0.0887 0.1868 0.3440 0.083 Uiso 1.00 1 c R . . H(6) H 0.0160 0.3039 0.3973 0.083 Uiso 1.00 1 c R . . H(7) H 0.0793 0.5583 0.4402 0.080 Uiso 1.00 1 c R . . H(8) H 0.0253 0.6438 0.4210 0.080 Uiso 1.00 1 c R . . H(9) H -0.0633 0.5160 0.4440 0.080 Uiso 1.00 1 c R . . H(10) H 0.0669 0.7276 0.3068 0.103 Uiso 1.00 1 c R . . H(11) H -0.0352 0.6767 0.2425 0.103 Uiso 1.00 1 c R . . H(12) H -0.0741 0.6829 0.3173 0.103 Uiso 1.00 1 c R . . H(13) H -0.0483 0.5177 0.1406 0.095 Uiso 1.00 1 c R . . H(14) H -0.1385 0.3699 0.1234 0.095 Uiso 1.00 1 c R . . H(15) H -0.1884 0.4604 0.1560 0.095 Uiso 1.00 1 c R . . H(16) H 0.7256 0.8140 0.3550 0.065 Uiso 1.00 1 c R . . H(17) H 0.7498 0.9409 0.3338 0.065 Uiso 1.00 1 c R . . H(18) H 0.7867 0.9412 0.4105 0.065 Uiso 1.00 1 c R . . H(19) H 0.5119 0.7030 0.5152 0.082 Uiso 1.00 1 c R . . H(20) H 0.5942 0.6822 0.4607 0.082 Uiso 1.00 1 c R . . H(21) H 0.6507 0.8105 0.5151 0.082 Uiso 1.00 1 c R . . H(22) H 0.3800 0.8105 0.5426 0.072 Uiso 1.00 1 c R . . H(23) H 0.2654 0.7892 0.4934 0.072 Uiso 1.00 1 c R . . H(24) H 0.2971 0.6792 0.4919 0.072 Uiso 1.00 1 c R . . H(25) H 0.3164 0.9772 0.4249 0.097 Uiso 1.00 1 c R . . H(26) H 0.3396 0.9746 0.3472 0.097 Uiso 1.00 1 c R . . H(27) H 0.2377 0.8513 0.3693 0.097 Uiso 1.00 1 c R . . H(28) H 0.6362 1.0062 0.2851 0.072 Uiso 1.00 1 c R . . H(29) H 0.4946 0.9669 0.2666 0.072 Uiso 1.00 1 c R . . H(30) H 0.5807 1.0863 0.3247 0.072 Uiso 1.00 1 c R . . H(31) H 0.0278 0.1420 0.0969 0.051 Uiso 1.00 1 c R . . H(32) H -0.0872 0.0762 -0.0135 0.071 Uiso 1.00 1 c R . . H(33) H -0.0774 0.2239 -0.0767 0.085 Uiso 1.00 1 c R . . H(34) H 0.0515 0.4430 -0.0301 0.078 Uiso 1.00 1 c R . . H(35) H 0.1626 0.5122 0.0826 0.057 Uiso 1.00 1 c R . . H(36) H 0.1488 0.2492 0.2995 0.077 Uiso 1.00 1 c R . . H(37) H 0.1545 0.0626 0.3126 0.128 Uiso 1.00 1 c R . . H(38) H 0.2254 -0.0365 0.2267 0.107 Uiso 1.00 1 c R . . H(39) H 0.2858 0.0457 0.1275 0.076 Uiso 1.00 1 c R . . H(40) H 0.2748 0.2285 0.1139 0.058 Uiso 1.00 1 c R . . H(41) H 0.3832 0.4605 0.1461 0.036 Uiso 1.00 1 c R . . H(42) H 0.3420 0.5643 0.1508 0.036 Uiso 1.00 1 c R . . H(43) H 0.5334 0.5644 0.3815 0.060 Uiso 1.00 1 c R . . H(44) H 0.6321 0.4589 0.4211 0.072 Uiso 1.00 1 c R . . H(45) H 0.6732 0.3222 0.3416 0.078 Uiso 1.00 1 c R . . H(46) H 0.6172 0.2931 0.2230 0.076 Uiso 1.00 1 c R . . H(47) H 0.5310 0.4119 0.1824 0.063 Uiso 1.00 1 c R . . H(48) H 0.7347 0.6674 0.2398 0.061 Uiso 1.00 1 c R . . H(49) H 0.8972 0.8059 0.1830 0.074 Uiso 1.00 1 c R . . H(50) H 0.8626 0.9328 0.1194 0.080 Uiso 1.00 1 c R . . H(51) H 0.6652 0.9192 0.1064 0.066 Uiso 1.00 1 c R . . H(52) H 0.5022 0.7830 0.1638 0.049 Uiso 1.00 1 c R . . H(53) H 0.6563 0.4560 0.0366 0.124 Uiso 1.00 1 c R . . H(54) H 0.7119 0.6594 0.0196 0.115 Uiso 1.00 1 c R . . H(55) H 0.5530 0.7024 -0.0161 0.135 Uiso 1.00 1 c R . . H(56) H 0.0651 -0.0687 0.3999 0.105 Uiso 1.00 1 c R . . H(57) H 0.1175 0.1464 0.4316 0.078 Uiso 1.00 1 c R . . H(58) H 0.0599 0.2146 0.5349 0.095 Uiso 1.00 1 c R . . H(59) H 0.5812 1.1578 0.0945 0.197 Uiso 1.00 1 c R . . H(60) H 0.4321 0.9493 0.0992 0.253 Uiso 1.00 1 c R . . H(61) H 0.3384 0.8122 -0.0016 0.186 Uiso 1.00 1 c R . .