# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 182/1410 data_global # 1. SUBMISSION DETAILS _publ_contact_author ; For X-ray structures: Jones, Peter G. Institut f\"ur Analytische und Anorganische Chemie Technische Universit\"at Braunschweig Postfach 3329 38023 Braunschweig Germany ; _publ_contact_author_phone '049 531 391-5382' _publ_contact_author_fax '049 531 391-5387' _publ_contact_author_email 'P.Jones@tu-bs.de' _publ_requested_journal 'Chem. Commun' _publ_requested_coeditor_name ? _publ_contact_letter ; ; #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Photochemical generated nitrilium phosphane-ylid tungsten complexes and their reactivity towards alkyne and nitrile derivates ; loop_ _publ_author_name _publ_author_address 'Streubel, Rainer' ; Institut f\"ur Analytische und Anorganische Chemie Technische Universit\"at Braunschweig Postfach 3329 38023 Braunschweig Germany ; 'Wilkens, Hendrik' ; Institut f\"ur Analytische und Anorganische Chemie Technische Universit\"at Braunschweig Postfach 3329 38023 Braunschweig Germany ; 'Ruthe, Frank' ; Institut f\"ur Analytische und Anorganische Chemie Technische Universit\"at Braunschweig Postfach 3329 38023 Braunschweig Germany ; 'Jones, Peter G.' ; Institut f\"ur Analytische und Anorganische Chemie Technische Universit\"at Braunschweig Postfach 3329 38023 Braunschweig Germany ; #============================================================================= data_wilkum _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C23 H29 N2 O7 P Si2 W' _chemical_formula_weight 716.48 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Si' 'Si' 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'W' 'W' -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.5466(10) _cell_length_b 10.7010(11) _cell_length_c 13.8717(14) _cell_angle_alpha 79.915(3) _cell_angle_beta 82.215(3) _cell_angle_gamma 75.406(3) _cell_volume 1484.8(3) _cell_formula_units_Z 2 _cell_measurement_temperature 143(2) _cell_measurement_reflns_used 6523 _cell_measurement_theta_min 2 _cell_measurement_theta_max 28 _exptl_crystal_description tablet _exptl_crystal_colour red _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.603 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 708 _exptl_absorpt_coefficient_mu 4.065 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.658 _exptl_absorpt_correction_T_max 0.962 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 143(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD' _diffrn_measurement_method \w-scan _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15748 _diffrn_reflns_av_R_equivalents 0.0269 _diffrn_reflns_av_sigmaI/netI 0.0262 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.50 _diffrn_reflns_theta_max 28.28 _reflns_number_total 7327 _reflns_number_gt 6896 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens XP' _computing_publication_material SHELXL-97 _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0267P)^2^+0.2143P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary Patterson _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment 'rigid methyls, others riding' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7327 _refine_ls_number_parameters 332 _refine_ls_number_restraints 25 _refine_ls_R_factor_all 0.0206 _refine_ls_R_factor_gt 0.0186 _refine_ls_wR_factor_ref 0.0438 _refine_ls_wR_factor_gt 0.0433 _refine_ls_goodness_of_fit_ref 1.019 _refine_ls_restrained_S_all 1.017 _refine_ls_shift/su_max 0.017 _refine_ls_shift/su_mean 0.000 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 W W 0.229097(7) 0.197247(7) 0.521790(5) 0.02010(3) Uani 1 1 d . . . P P 0.14385(4) 0.20871(4) 0.69827(3) 0.01815(9) Uani 1 1 d . . . Si1 Si -0.05909(6) 0.40192(5) 0.82385(4) 0.02818(12) Uani 1 1 d . . . Si2 Si -0.13028(5) 0.14615(6) 0.76806(4) 0.02726(11) Uani 1 1 d . . . N1 N 0.18428(15) 0.05692(15) 0.76417(11) 0.0206(3) Uani 1 1 d U . . N2 N 0.33344(16) 0.15972(15) 0.81257(12) 0.0234(3) Uani 1 1 d U . . C1 C 0.3031(2) 0.1779(2) 0.38244(17) 0.0338(5) Uani 1 1 d . . . O1 O 0.3459(2) 0.1669(2) 0.30304(13) 0.0557(5) Uani 1 1 d . . . C2 C 0.4127(2) 0.1856(2) 0.55901(16) 0.0337(5) Uani 1 1 d . . . O2 O 0.51498(18) 0.1790(3) 0.58037(16) 0.0593(6) Uani 1 1 d . . . C3 C 0.2595(2) -0.0022(2) 0.55741(16) 0.0301(4) Uani 1 1 d . . . O3 O 0.27730(19) -0.11249(16) 0.57881(14) 0.0443(4) Uani 1 1 d . . . C4 C 0.0447(2) 0.2126(2) 0.48381(15) 0.0272(4) Uani 1 1 d . . . O4 O -0.05824(17) 0.22419(18) 0.46135(13) 0.0412(4) Uani 1 1 d . . . C5 C 0.1959(2) 0.3947(2) 0.48858(15) 0.0298(4) Uani 1 1 d . . . O5 O 0.17692(19) 0.50564(16) 0.46624(13) 0.0421(4) Uani 1 1 d . . . C6 C 0.26380(18) 0.25921(17) 0.76200(13) 0.0211(3) Uani 1 1 d U . . C7 C 0.28475(18) 0.04619(18) 0.81102(13) 0.0207(3) Uani 1 1 d U . . C8 C -0.02874(18) 0.27733(18) 0.73516(14) 0.0225(4) Uani 1 1 d . . . H8 H -0.0631 0.3301 0.6732 0.027 Uiso 1 1 calc R . . C9 C -0.0061(2) 0.5511(2) 0.75715(19) 0.0382(5) Uani 1 1 d . . . H9A H -0.0802 0.6113 0.7254 0.046 Uiso 1 1 calc R . . H9B H 0.0667 0.5259 0.7071 0.046 Uiso 1 1 calc R . . H9C H 0.0230 0.5942 0.8040 0.046 Uiso 1 1 calc R . . C10 C 0.0276(3) 0.3308(3) 0.93750(16) 0.0413(5) Uani 1 1 d . . . H10A H -0.0219 0.3719 0.9933 0.050 Uiso 1 1 calc R . . H10B H 0.1163 0.3468 0.9274 0.050 Uiso 1 1 calc R . . H10C H 0.0337 0.2366 0.9511 0.050 Uiso 1 1 calc R . . C11 C -0.2377(3) 0.4602(3) 0.8601(2) 0.0539(7) Uani 1 1 d . . . H11A H -0.2507 0.5275 0.9025 0.065 Uiso 1 1 calc R . . H11B H -0.2729 0.3868 0.8959 0.065 Uiso 1 1 calc R . . H11C H -0.2838 0.4969 0.8010 0.065 Uiso 1 1 calc R . . C12 C -0.0782(2) 0.0143(2) 0.68902(18) 0.0372(5) Uani 1 1 d . . . H12A H 0.0161 -0.0249 0.6918 0.045 Uiso 1 1 calc R . . H12B H -0.0953 0.0513 0.6210 0.045 Uiso 1 1 calc R . . H12C H -0.1279 -0.0529 0.7128 0.045 Uiso 1 1 calc R . . C13 C -0.1203(2) 0.0690(3) 0.89886(16) 0.0381(5) Uani 1 1 d . . . H13A H -0.1757 0.0058 0.9145 0.046 Uiso 1 1 calc R . . H13B H -0.1510 0.1365 0.9418 0.046 Uiso 1 1 calc R . . H13C H -0.0288 0.0242 0.9091 0.046 Uiso 1 1 calc R . . C14 C -0.3050(2) 0.2285(3) 0.7458(2) 0.0508(7) Uani 1 1 d . . . H14A H -0.3574 0.1629 0.7549 0.061 Uiso 1 1 calc R . . H14B H -0.3080 0.2752 0.6784 0.061 Uiso 1 1 calc R . . H14C H -0.3410 0.2906 0.7924 0.061 Uiso 1 1 calc R . . C15 C 0.35626(18) -0.07852(17) 0.86224(13) 0.0218(3) Uani 1 1 d U . . C16 C 0.3183(2) -0.19391(19) 0.85848(15) 0.0286(4) Uani 1 1 d U . . H16 H 0.2479 -0.1918 0.8216 0.034 Uiso 1 1 calc R . . C17 C 0.3834(2) -0.3106(2) 0.90852(17) 0.0340(5) Uani 1 1 d U . . H17 H 0.3583 -0.3890 0.9054 0.041 Uiso 1 1 calc R . . C18 C 0.4851(2) -0.3141(2) 0.96314(16) 0.0320(4) Uani 1 1 d U . . H18 H 0.5275 -0.3943 0.9990 0.038 Uiso 1 1 calc R . . C19 C 0.5253(2) -0.2015(2) 0.96581(16) 0.0323(4) Uani 1 1 d U . . H19 H 0.5961 -0.2046 1.0025 0.039 Uiso 1 1 calc R . . C20 C 0.4614(2) -0.08293(19) 0.91432(15) 0.0281(4) Uani 1 1 d U . . H20 H 0.4898 -0.0056 0.9149 0.034 Uiso 1 1 calc R . . C21 C 0.29978(19) 0.38805(18) 0.75490(15) 0.0247(4) Uani 1 1 d U . . C22 C 0.3362(2) 0.57708(19) 0.64618(17) 0.0319(4) Uani 1 1 d U . . H22A H 0.2868 0.6265 0.6989 0.038 Uiso 1 1 calc R . . H22B H 0.3057 0.6250 0.5826 0.038 Uiso 1 1 calc R . . C23 C 0.4803(3) 0.5683(3) 0.6456(2) 0.0501(7) Uani 1 1 d U . . H23A H 0.5090 0.5272 0.7104 0.060 Uiso 1 1 calc R . . H23B H 0.4967 0.6561 0.6305 0.060 Uiso 1 1 calc R . . H23C H 0.5296 0.5157 0.5956 0.060 Uiso 1 1 calc R . . O6 O 0.31536(18) 0.43010(15) 0.82623(12) 0.0383(4) Uani 1 1 d . . . O7 O 0.30897(14) 0.44673(13) 0.66224(10) 0.0265(3) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 W 0.02349(4) 0.01836(4) 0.01952(4) -0.00441(3) -0.00122(3) -0.00617(3) P 0.0218(2) 0.0152(2) 0.0186(2) -0.00218(16) -0.00436(16) -0.00526(16) Si1 0.0304(3) 0.0232(3) 0.0296(3) -0.0074(2) 0.0037(2) -0.0049(2) Si2 0.0252(3) 0.0307(3) 0.0281(3) -0.0021(2) -0.0047(2) -0.0110(2) N1 0.0247(7) 0.0169(7) 0.0209(7) -0.0015(6) -0.0040(6) -0.0060(6) N2 0.0274(8) 0.0185(7) 0.0264(8) -0.0034(6) -0.0073(6) -0.0065(6) C1 0.0342(11) 0.0387(12) 0.0329(11) -0.0107(9) 0.0012(8) -0.0154(9) O1 0.0627(12) 0.0810(15) 0.0329(9) -0.0251(9) 0.0151(8) -0.0329(11) C2 0.0301(11) 0.0407(12) 0.0306(11) -0.0125(9) 0.0014(8) -0.0062(9) O2 0.0266(9) 0.1004(18) 0.0567(12) -0.0350(12) -0.0029(8) -0.0099(10) C3 0.0327(10) 0.0264(10) 0.0318(10) -0.0114(8) 0.0022(8) -0.0062(8) O3 0.0529(11) 0.0215(8) 0.0556(11) -0.0099(7) 0.0067(8) -0.0069(7) C4 0.0340(10) 0.0250(9) 0.0246(9) -0.0072(7) -0.0027(8) -0.0084(8) O4 0.0343(9) 0.0452(10) 0.0479(10) -0.0094(8) -0.0153(7) -0.0085(7) C5 0.0369(11) 0.0298(11) 0.0252(9) -0.0039(8) -0.0077(8) -0.0102(9) O5 0.0629(11) 0.0232(8) 0.0423(9) 0.0032(7) -0.0188(8) -0.0118(8) C6 0.0263(9) 0.0166(8) 0.0219(8) -0.0044(6) -0.0044(7) -0.0054(7) C7 0.0252(9) 0.0171(8) 0.0201(8) -0.0022(6) -0.0043(7) -0.0048(7) C8 0.0214(8) 0.0232(9) 0.0222(8) -0.0014(7) -0.0039(7) -0.0041(7) C9 0.0376(12) 0.0233(10) 0.0507(14) -0.0036(9) -0.0009(10) -0.0047(9) C10 0.0609(16) 0.0415(13) 0.0256(10) -0.0098(9) -0.0028(10) -0.0168(12) C11 0.0409(14) 0.0428(15) 0.0729(19) -0.0198(14) 0.0196(13) -0.0060(11) C12 0.0446(13) 0.0383(12) 0.0384(12) -0.0094(10) -0.0051(10) -0.0242(10) C13 0.0437(13) 0.0426(13) 0.0297(11) -0.0002(9) 0.0017(9) -0.0197(10) C14 0.0317(12) 0.0537(16) 0.0704(19) -0.0069(14) -0.0165(12) -0.0114(11) C15 0.0268(9) 0.0171(8) 0.0203(8) -0.0031(6) -0.0027(7) -0.0025(7) C16 0.0399(11) 0.0197(9) 0.0279(10) -0.0029(7) -0.0101(8) -0.0071(8) C17 0.0485(13) 0.0185(9) 0.0353(11) -0.0031(8) -0.0098(9) -0.0061(9) C18 0.0392(11) 0.0198(9) 0.0307(10) 0.0000(8) -0.0057(8) 0.0035(8) C19 0.0314(10) 0.0281(10) 0.0348(11) -0.0023(8) -0.0125(8) 0.0010(8) C20 0.0336(10) 0.0199(9) 0.0310(10) -0.0017(7) -0.0099(8) -0.0044(8) C21 0.0259(9) 0.0170(8) 0.0326(10) -0.0013(7) -0.0089(7) -0.0060(7) C22 0.0380(11) 0.0176(9) 0.0430(12) 0.0007(8) -0.0082(9) -0.0128(8) C23 0.0398(13) 0.0352(13) 0.077(2) 0.0063(13) -0.0106(13) -0.0188(11) O6 0.0600(10) 0.0277(8) 0.0358(8) -0.0060(6) -0.0164(7) -0.0191(7) O7 0.0322(7) 0.0169(6) 0.0324(7) -0.0012(5) -0.0053(6) -0.0101(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag W C1 2.010(2) . ? W C5 2.032(2) . ? W C2 2.039(2) . ? W C4 2.043(2) . ? W C3 2.057(2) . ? W P 2.5039(5) . ? P N1 1.7007(16) . ? P C8 1.8221(19) . ? P C6 1.8678(19) . ? Si1 C11 1.858(3) . ? Si1 C9 1.873(2) . ? Si1 C10 1.876(3) . ? Si1 C8 1.910(2) . ? Si2 C13 1.862(2) . ? Si2 C12 1.867(2) . ? Si2 C14 1.873(3) . ? Si2 C8 1.930(2) . ? N1 C7 1.287(2) . ? N2 C6 1.284(2) . ? N2 C7 1.438(2) . ? C1 O1 1.146(3) . ? C2 O2 1.139(3) . ? C3 O3 1.139(3) . ? C4 O4 1.141(3) . ? C5 O5 1.146(3) . ? C6 C21 1.504(3) . ? C7 C15 1.470(2) . ? C15 C20 1.390(3) . ? C15 C16 1.402(3) . ? C16 C17 1.381(3) . ? C17 C18 1.384(3) . ? C18 C19 1.381(3) . ? C19 C20 1.399(3) . ? C21 O6 1.202(2) . ? C21 O7 1.330(2) . ? C22 O7 1.467(2) . ? C22 C23 1.498(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 W C5 90.58(9) . . ? C1 W C2 90.22(9) . . ? C5 W C2 91.15(9) . . ? C1 W C4 89.75(8) . . ? C5 W C4 87.80(8) . . ? C2 W C4 178.95(8) . . ? C1 W C3 90.38(9) . . ? C5 W C3 178.86(8) . . ? C2 W C3 89.47(9) . . ? C4 W C3 91.59(8) . . ? C1 W P 176.84(7) . . ? C5 W P 92.34(6) . . ? C2 W P 88.51(6) . . ? C4 W P 91.57(6) . . ? C3 W P 86.72(6) . . ? N1 P C8 106.90(8) . . ? N1 P C6 89.05(8) . . ? C8 P C6 114.95(9) . . ? N1 P W 109.05(6) . . ? C8 P W 121.98(6) . . ? C6 P W 109.65(6) . . ? C11 Si1 C9 104.64(12) . . ? C11 Si1 C10 109.00(14) . . ? C9 Si1 C10 112.28(12) . . ? C11 Si1 C8 111.24(12) . . ? C9 Si1 C8 108.43(10) . . ? C10 Si1 C8 111.09(10) . . ? C13 Si2 C12 108.25(12) . . ? C13 Si2 C14 110.27(13) . . ? C12 Si2 C14 106.33(13) . . ? C13 Si2 C8 111.04(10) . . ? C12 Si2 C8 113.35(10) . . ? C14 Si2 C8 107.48(11) . . ? C7 N1 P 110.08(13) . . ? C6 N2 C7 109.56(16) . . ? O1 C1 W 179.7(2) . . ? O2 C2 W 179.6(2) . . ? O3 C3 W 178.6(2) . . ? O4 C4 W 178.28(19) . . ? O5 C5 W 177.44(18) . . ? N2 C6 C21 117.48(17) . . ? N2 C6 P 110.61(13) . . ? C21 C6 P 131.53(14) . . ? N1 C7 N2 119.60(16) . . ? N1 C7 C15 123.27(17) . . ? N2 C7 C15 117.11(16) . . ? P C8 Si1 115.04(10) . . ? P C8 Si2 112.46(10) . . ? Si1 C8 Si2 115.86(10) . . ? C20 C15 C16 119.73(18) . . ? C20 C15 C7 120.49(17) . . ? C16 C15 C7 119.78(17) . . ? C17 C16 C15 119.8(2) . . ? C16 C17 C18 120.3(2) . . ? C19 C18 C17 120.42(19) . . ? C18 C19 C20 119.8(2) . . ? C15 C20 C19 119.83(19) . . ? O6 C21 O7 126.18(18) . . ? O6 C21 C6 122.27(18) . . ? O7 C21 C6 111.53(16) . . ? O7 C22 C23 111.04(18) . . ? C21 O7 C22 116.73(16) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.142 _refine_diff_density_min -0.539 _refine_diff_density_rms 0.092 #end of cif data for excal #============================================================================= #eof # End of Crystallographic Information File