S1 The SUPERBULKY Pn LIGAND COMPLEXES [CpBIGFe(η5-P5)] and [(CpBIGFe)2(η4:4P4)] – SYNTHESIS AND CHARACTERIZATION Sebsatian Heinl, Gabor Balazs and Manfred Scheer* Institut für Anorganische Chemie, Universitätsstraße 31, 93053 Regensburg, Email: Manfred.Scheer@chemie.uni-regensburg.de 1. Crystallographic details The crystal structure analyses were performed either on an Oxford Diffraction Gemini R Ultra CCD diffractometer (1b, 4) or an Oxford Diffraction SuperNova diffractometer (3). For all compounds an analytical absorption correction was carried out.[1] The structures were solved by direct methods either of the program SIR-92[2] or SHELXS-97[3] and refined with least square method on F2 employing SHELXL-97 with anisotropic displacements for non-H atoms. Hydrogen atoms were located in idealized positions and refined isotropically according to the riding model. CCDC-982098 (1b), CCDC-982099 (3) and CCDC-982100 (4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: + 44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk). S2 Crystal data for 1b: C55H65FeP5, M = 936.77, space group P1;¯ (no.2), a = 13.8286(11) Å, b = 13.8982(8) Å, c = 14.6573(8) Å, α = 96.579(4)°, β = 106.372(6)°, γ = 103.405(6)°, V = 2579.9(3) Å3, Z = 2, μ = 4.061 mm-1, F(000) = 992.0, T = 123 K, 24959 reflections measured, 9182 unique (Rint = 0.0365), R1 = 0.0578, wR2 = 0.1457 for I > 2σ(I); CCDC-982098. Figure S 1: Molecular structure of 1b in the crystal. H atoms and disorder are omitted for clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å] and angles [°]: P1-P2 2.105(1), P2-P3 2.107(1), P3-P4 2.108(1), P4-P5 2.106(1), P1-P5 2.109(1), FeP5,centroid 1.5537(5), Fe-Cpcentroid 1.7281(5), Fe-P5,centroid- Fe-Cpcentroid 179.44(3). S3 Crystal data for 3 · 2 C7H8: C128H146Fe2O4, M = 1860.15, space group P21/c (no.14), a = 11.6361(3) Å, b = 24.0846(5) Å, c = 18.4036(4) Å, β = 99.730(2)°, V = 5083.4(2) Å3, Z = 2, μ = 2.708 mm-1, F(000) = 1996.0, T = 123 K, 80290 reflections measured, 10561 unique (Rint = 0.0334), R1 = 0.0373, wR2 = 0.0935 for I > 2σ(I); CCDC-982099. Figure S 2: Molecular structure of 3 in the crystal. H atoms, solvent molecules and disorder are omitted for clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å] and angles [°]: Fe1-Fe1’ 2.6180(3), Fe1-C1 1.756(2), Fe1-C2 1.950(2), Fe1-C2’ 1.950(2), FeCpcentroid 1.8055(2), C1-Fe1-Fe1’ 94,38(5), Fe1-C2-Fe1’ 84.60(5), C2-Fe1-C2’ 95,40(6). S4 Table S 1 Fe-Fe bond lengths of selected of trans-[CpRFe(CO)2]2 complexes. CpR Fe-Fe bond length [Å] CpBIG, C5(4-nBuC6H4)5, (3) 2.6180(3) Cp, C5H5 2.534(2)4 Cp*, C5Me5 2.560(1)5 Cp’, C5H4tBu 2.550(1)6 CpiPr, C5iPr5 2.600(2)7 CpBn, C5(CH2Ph)5 2.5718(1)8 The Cambridge Crystallographic Data Centre was searched through for trans-[CpRFe(CO)2]2 complexes and no longer Fe-Fe bond length than in case of 3 was found. S5 Crystal data for 4 · 0.5 CH2Cl2 · CH3CN: C112.5H134ClFe2NP4, M = 1771.25, space group P1;¯ (no.2), a = 16.3602(5) Å, b = 16.8056(5) Å, c = 21.5861(5) Å, α = 73.085(2)°, β = 71.808(2)°, γ = 61.207(3)°, V = 4870.3(3) Å3, Z = 2, μ = 3.619 mm-1, F(000) = 1890.0, T = 124 K, 35298 reflections measured, 18851 unique (Rint = 0.0253), R1 = 0.0797, wR2 = 0.1711 for I > 2σ(I); CCDC-982100. Figure S 3 Molecular structure of 4 in the crystal. H atoms, solvent molecules and disorder are omitted for clarity; thermal ellipsoids drawn at 50% probability level. Selected bond lengths [Å]: P1-P2 2.100(2), P2-P3 2.3684(2), P3-P4 2.098(2), P1∙∙∙P4 3.560(2), Fe1-Fe2 2.6307(6). Selected angle [°]: CpPlane-CpPlane 22.0(2). S6 Table S 2 Comparison of selected bond lengths [Å] of [(CpRFe)2(µ,η4:4-P4)] complexes. CpR Fe1-Fe2 P1-P2 P2-P3 P3-P4 P1∙∙∙P4 2.6307(6) 2.100(2) 2.3684(2) 2.098(2) 3.560(2) Cp’’, C5H3tBu2[9] 2.616(1) 2.081(2) 2.385(2) 2.094(2) 3.57 Cp’’’, C5H2tBu3[10] 2.6430(8) 2.0877(13) 2.368(2) 2.0877(13) 3.55 2.603(1) 2.090(2) 2.436(2) 2.093(2) 3.550(2) 4: CpBIG, C5(4-nBuC6H4)5 Cp2Si, C5H3(SiMe3)2[11] S7 2. Computational details All calculations have been performed with the TURBOMOLE program package.[ 12 ] The geometries have been optimized without any symmetry restrains at the RI-[13]B3LYP[14]/def2TZVP[15] level of theory including the Multipole Accelerated Resolution of Identity (MARI-J) approximation[ 16 ]. To obtain the orbital energies single point calculations without the RI approximation have been performed. Table S 4. Calculated orbital energies and HOMO-LUMO gap for [CpRFe(η5-P5)] at the B3LYP/def2-TZVP level of theory. HOMO-LUMO (eV) 4.304 HOMO (eV) LUMO (eV) -6.339 -2.035 C5H4Ph 4.141 -6.264 -2.123 C5H3Ph2 4.043 -6.196 -2.153 C5H2Ph3 4.017 -6.166 -2.149 C5HPh4 4.072 -6.187 -2.115 C5Ph5 4.071 -6.164 -2.093 C5H4(CF3) 4.182 -6.563 -2.382 C5H3(CF3)2 4.063 -6.761 -2.699 C5H2(CF3)3 3.965 -6.938 -2.973 C5H(CF3)4 3.881 -7.079 -3.199 C5(CF3)5 3.795 -7.211 -3.426 C5(CH3)5 4.414 -6.149 -1.735 CpR C5H5 S8 Figure S 4: Calculated orbital energies (eV) for [CpRFe(η5-P5)] at the B3LYP/def2-TZVP level of theory. S9 Figure S 5: Calculated orbital energies (eV) for [CpRFe(η5-P5)] at the B3LYP/def2-TZVP level of theory. S 10 Figure S 6: Isosurfaces of the HOMO and LUMO orbitals in [{C5(C6H5)5}Fe(η5-P5)] calculated at the B3LYP/def2-TZVP level of theory. S 11 Figure S 6: Isosurfaces of the HOMO and LUMO orbitals in [{C5(CF3)5}Fe(η5-P5)] calculated at the B3LYP/def2-TZVP level of theory. S 12 Table S 5. Cartesian coordinates of the optimized geometry of [{C5(C6H5)5}Fe(η5-P5)] at the B3LYP/def2-TZVP level of theory. Atom Fe P P P P P C C C C C C C C C C C C C C C C C C C C C H C H C H C H C H C H C H C H C H C H x 0.7502552 3.1084942 2.5815462 0.9042203 0.3950688 1.7568419 -0.5972412 -1.2986193 -0.6637486 0.4302042 0.4713604 -1.0353828 -2.5821782 -1.1841911 1.2290059 1.3215484 -2.3619661 -0.1575739 -2.7655593 -3.6824554 -1.4300027 -1.5178188 1.2875490 1.8628300 0.7098490 2.7074777 -2.7969952 -3.0591574 -0.5935075 0.8759651 -4.0006436 -1.9387273 -4.9192013 -3.5728700 -1.9796724 -1.1951906 -2.0628784 -1.3562556 1.9651379 0.7937093 2.5443872 1.8189391 1.4597548 -0.3627713 3.4577584 3.2039984 y 1.0551418 1.6195685 0.4513704 1.3567473 3.0849382 3.2469258 -0.6217800 0.5691337 1.0888695 0.2196799 -0.8377846 -1.5801922 1.0469888 2.1944431 0.2804425 -2.0536644 -2.0284652 -2.1210312 1.2489016 1.2281619 1.9544313 3.4490376 -0.8494333 1.4478146 -3.3131733 -1.9958255 -2.9763673 -1.6379666 -3.0652710 -1.8066617 1.6337292 1.0994079 1.6085562 1.0645819 2.9385634 0.9877362 4.4345019 3.6563429 -0.8153426 -1.7619501 1.4805626 2.3402195 -4.4738880 -3.3868116 -3.1562564 -1.0368897 z . 4.3306602 4.5335959 2.8463175 1.9211674 3.0362151 4.6512092 4.3787849 4.7724189 5.9519626 6.2873614 5.3151920 3.3312127 4.1960318 6.7974952 7.5388277 5.3971129 3.3320675 2.3872806 2.8250654 5.0429753 8.1549528 6.2791113 8.3639214 7.9742922 5.3836383 5.5699359 2.4142378 4.0607766 1.4668249 2.3745841 2.3197386 2.1458898 4.5370562 6.1063859 8.9670664 8.5791943 7.0919121 5.2311513 9.5763144 8.0588117 9.1839158 7.3668555 5.5272621 5.2663910 5.7087636 5.6026001 S 13 C H H C H H C H H C H H C H H H H H H H -1.9152985 -3.8279033 0.1051377 -5.0828911 -4.1151003 -5.7548212 -2.2943034 -2.1611153 -2.3073226 2.6011616 1.9945308 3.0319376 2.8386857 0.9625648 4.5308038 -6.0450935 -2.7181479 3.1337242 3.4250600 -2.2541930 -3.4960984 -3.3074215 -3.4648841 1.8178772 1.7894056 1.7411982 4.1856343 2.7274646 5.4002132 0.3492562 -1.7024722 2.3958043 -4.4008662 -5.4359109 -3.0847592 2.1191614 4.9553619 0.3759067 -5.3049542 -4.2316061 1.4737707 2.4364936 0.7423028 3.1727200 1.2541850 5.2130785 8.4399769 10.0136633 6.6671909 9.9899394 10.1968070 9.4959290 5.6858305 5.5146245 5.8360291 2.7776110 9.0729009 10.9324887 5.7931778 0.7548199 S 14 Table S 6. Cartesian coordinates of the optimized geometry of [{C5(CF3)5}Fe(η5-P5)] at the B3LYP/def2-TZVP level of theory. Atom Fe P P P P P C C C C C C F F F C F F F C F F F C F F F C F F F x 0.7893969 3.1554205 2.5910756 0.8803867 0.3877711 1.7935987 -0.5245223 -1.2178088 -0.5723379 0.5348413 0.5802701 -1.1225389 -1.1549181 -2.3785475 -0.4160340 -0.9974161 -0.1635993 -1.1217809 -2.2004644 1.5469219 2.8286582 1.2558457 1.4615887 -2.5086695 -2.8069606 -2.4490164 -3.5354677 1.3645104 1.9619196 0.5578976 2.3212331 y 1.1277194 1.7119934 0.5636267 1.4715378 3.1814262 3.3281540 -0.5591116 0.6260425 1.1416733 0.2864236 -0.7499572 2.2793331 3.4577780 1.9694895 2.4646258 -1.5904731 -1.7317495 -2.7844235 -1.2969577 -1.9338219 -1.5647636 -2.7628935 -2.6406004 1.1540182 2.3880538 1.2053556 0.3579949 0.3586009 1.5450217 0.1347988 -0.5700298 z . 4.2638311 4.4086392 2.7148207 1.8487935 3.0037557 4.5875622 4.3226942 4.7259280 5.8974023 6.2045090 5.2152080 6.7603807 6.1265741 7.1361569 7.8771056 3.2950737 2.2586360 3.9064604 2.7957117 5.2010837 5.3157917 6.2198970 4.0700249 4.1040051 4.5188321 2.7664927 4.4519575 7.4860297 7.6539030 8.5411511 7.5344170 S 15 Figure S 7: IR spectrum of [CpBIGFe(CO)2]2 (1b) in toluene. νCO [cm-1] are assigned. 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