Supporting Information Cyclo-P 3 Complexes of Vanadium. Redox Properties and Origin of the 31 P NMR Chemical Shift. Balazs Pinter,, Kyle T. Smith, Masahiro Kamitani, Eva M. Zolnhofer,ǁ Ba L. Tran, Skye Fortier, Maren Pink, Gang Wu, Brian C. Manor, Karsten Meyer,ǁ Mu-Hyun Baik,,±,* and Daniel J. Mindiola,* Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, IN 47405 (USA). Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels (Belgium) Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia PA, 19104 (USA). ǁ Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich Alexander University Erlangen - Nürnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany. Department of Chemistry, Queen's University, Kingston, Ontario, Canada K7L 3N6. ± Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon, Korea. E-mail: mindiola@sas.upenn.edu, mbaik2805@kaist.ac.kr Table of Contents Materials and Methods S2-S3 NMR Spectroscopic Data of Isolated Compounds 1 H NMR & 31 P NMR Spectra of 2 S4 1 H NMR Spectrum of 3 S5 1 H NMR Spectrum of [CoCp * 2][1] S5 Crystallographic Details Complex 2 Complex 3 Complex [CoCp * 2][1] Theoretical Calculations (coordinates) References S6-S7 S7-S8 S8-S9 S10-S16 S17 S1
Materials and Methods 31 P{ 1 H}, and 1 H{ 31 P} NMR were recorded on a Bruker UNI400 Fourier transform NMR spectrometer. 1 H chemical shifts are reported referenced to the internal residual proton resonance of C 6 D 6 (δ = 7.160 ppm). 31 P{1H} NMR chemical shifts are reported with respect to external H 3 PO 4 (δ 0.0 ppm). For 2, X-ray intensity data were collected on a Bruker APEXII CCD area detector employing graphite-monochromated Mo-Ka radiation (l=0.71073 Å) at a temperature of 100(1)K. Preliminary indexing was performed from a series of thirty-six 0.5 rotation frames with exposures of 10 seconds. A total of 1981 frames were collected with a crystal to detector distance of 45.0 mm, rotation widths of 0.5 and exposures of 30 seconds. Rotation frames were integrated using SAINT 1, producing a listing of unaveraged F2 and s(f2) values which were then passed to the SHELXTL 2 program package for further processing and structure solution. A total of 61102 reflections were measured over the ranges 1.56 q 27.51, -17 h 17, -22 k 20, -25 l 21 yielding 10441 unique reflections (Rint = 0.0460). For 3, X-ray intensity data were collected on a Bruker APEXII CCD area detector employing graphite-monochromated Mo- Ka radiation (l=0.71073 Å) at a temperature of 100(1)K. Preliminary indexing was performed from a series of thirty-six 0.5 rotation frames with exposures of 10 seconds. A total of 2573 frames were collected with a crystal to detector distance of 37.5 mm, rotation widths of 0.5 and exposures of 5 seconds. Rotation frames were integrated using SAINT 1, producing a listing of unaveraged F2 and s(f2) values which were then passed to the SHELXTL 2 program package for further processing and structure solution. A total of 195035 reflections were measured over the ranges 1.49 q 27.57, -20 h 19, -34 k 34, -25 l 25 yielding 18634 unique reflections (Rint = 0.0472). For [CoCp * 2][1], A black crystal (approximate dimensions 0.22 0.10 0.07 mm 3 ) was placed onto the tip of a 0.1 mm diameter glass capillary and mounted on a Bruker APEX II Kappa Duo diffractometer equipped with an APEX II detector at 150(2) K. The data collection was carried out using Mo Kα radiation (graphite monochromator) with a frame time of 20 seconds and a detector distance of 5.00 cm. A collection strategy was calculated and complete data to a resolution of 0.71 Å with a redundancy of 4 were collected. Ten major sections of frames were collected with 0.50º ω and φ scans. Data to a resolution of 0.80 Å were considered in the reduction. Final cell constants were calculated from the xyz centroids of 9821 strong reflections from the actual data collection after integration (SAINT) 1. The intensity data S2
were corrected for absorption (SADABS) 3. The space group P-1 was determined based on intensity statistics and the lack of systematic absences. The structure was solved using SIR-2004 4 and refined with SHELXL-97 2. A direct-methods solution was calculated, which provided most non-hydrogen atoms from the E-map. Full-matrix least squares / difference Fourier cycles were performed, which located the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. The final full matrix least squares refinement converged to R1 = 0.0439 and wr2 = 0.1202 (F2, all data). The remaining electron density peak is located near a disordered site. EPR spectra were recorded on a JEOL continuous wave spectrometer JES-FA200 equipped with an X-band Gunn oscillator bridge, a cylindrical mode cavity, and a helium cryostat. The solutions were freshly prepared in airtight J. Young quartz EPR tubes in an MBraun inert-gas glovebox containing an atmosphere of purified dinitrogen. The tubes were frozen in liquid nitrogen upon exiting the glovebox and kept frozen until measured. Background spectra were obtained on clean solvents at the same measurement conditions. Spectral simulation was performed using the program W95EPR 5 written by F. Neese. S3
Figure S1. 1 H NMR Spectrum of 2 (25 C, 400 MHz, tolune-d 8 ). Residual solvent has been labeled. Figure S2. 31 P{ 1 H} NMR Spectrum of 2 (25 C, 400 MHz, toluene-d 8 ). S4
Figure S3. 1 H NMR Spectrum of 3 (25 C, 400 MHz, C 6 D 6 ). Residual solvent and small impurities have been labeled. Figure S4. 1 H NMR Spectrum of [CoCp * 2][1] (25 C, 400 MHz, THF-d 8 ). Residual solvent has been labeled. S5
Table S1. Summary of Structure Determination of 2 Empirical formula C 46 H 70 N 2 OP 2.55 Cl 0.15 V Formula weight 802.27 Temperature 100(1) K Wavelength 0.71073 Å Crystal system monoclinic Space group P2 1 /n Cell constants: a 13.1916(10) Å b 17.3669(13) Å c 19.9287(16) Å β 90.145(3) Volume 4565.6(6) Å3 Z 4 Density (calculated) 1.167 Mg/m3 Absorption coefficient 0.350 mm-1 F(000) 1727 Crystal size 0.32 x 0.25 x 0.20 mm 3 Theta range for data collection 1.56 to 27.51 Index ranges -17 h 17, -22 k 20, -25 l 21 Reflections collected 61102 Independent reflections 10441 [R(int) = 0.0460] Completeness to theta = 27.51 99.5 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.6540 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10441 / 0 / 504 Goodness-of-fit on F2 1.098 S6
Final R indices [I>2sigma(I)] R1 = 0.0667, wr2 = 0.1305 R indices (all data) R1 = 0.0966, wr2 = 0.1479 Largest diff. peak and hole 0.657 and -0.558 e.å -3 Table S2. Summary of Structure Determination of 3 Empirical formula C 90 H 120 N 6 P 3 OV 2 Formula weight 1496.71 Temperature Wavelength Crystal system 100(1) K 0.71073 Å monoclinic Space group P2 1 /n Cell constants: a b c 16.056(2) Å 26.236(4) Å 19.263(3) Å β 90.609(9) Volume 8114(2) Å3 Z 4 Density (calculated) 1.225 Mg/m 3 Absorption coefficient 0.340 mm-1 F(000) 3204 Crystal size 0.50 x 0.20 x 0.10 mm3 Theta range for data collection 1.49 to 27.57 Index ranges -20 h 19, -34 k 34, -25 l 25 Reflections collected 195035 Independent reflections 18634 [R(int) = 0.0472] S7
Completeness to theta = 27.57 99.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.7031 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 18634 / 31 / 935 Goodness-of-fit on F 2 1.022 Final R indices [I>2sigma(I)] R1 = 0.0532, wr2 = 0.1369 R indices (all data) R1 = 0.0788, wr2 = 0.1566 Largest diff. peak and hole 1.463 and -0.660 e.å -3 Table S3. Summary of Structure Determination of [CoCp * 2][1] Empirical formula C 78 H 103.50 CoN 3 O 0.25 P 3 V Formula weight 1289.92 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Cell constants: a 14.9860(4) Å b 22.3994(7)Å c 23.3004(7)Å α 108.043(2) β 96.706(2 ) γ 101.488(2) Volume 7152.9(4) Å3 Z 4 Density (calculated) 1.198 Mg/m3 Absorption coefficient 0.474 mm-1 S8
F(000) 2758 Crystal size 0.22 0.10 0.07mm3 Theta range for data collection 1.41 to 26.42 Index ranges -18 h 18, -28 k 28, -2 9 l 29 Reflections collected 125997 Independent reflections 29334 [R(int) = 0.0425] Completeness to theta = 27.57 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9676 and 0.9030 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 29334 / 321 / 1660 Goodness-of-fit on F 2 1.013 Final R indices [I>2sigma(I)] R1 = 0.0439, wr2 = 0.1047 R indices (all data) R1 = 0.0788, wr2 = 0.1566 Largest diff. peak and hole 1.265 and -0.464 e.å-3 S9
Theoretical Calculations Cartesian coordinates of the optimized structures. Values are in Å. 1 V 0.000000000 0.000000000 0.000000000 P 1.885906100 0.233405411 1.581496239 P 0.210392341 1.569427729 1.884332538 P 1.583758116 1.877223372 0.219081849 N -0.751906574 0.956922889-1.630719781 N -1.826420307-0.410595655 0.805074990 N 0.937249064-1.576536059-0.665466726 C -0.850308895-2.785337210 2.301402092 H -0.039481811-2.425251722 1.663798213 C -1.623827934-1.660341144 2.945348740 C -1.912871361-1.737998009 4.314038277 H -1.546087265-2.593287468 4.875694752 C -2.656652689-0.754531622 4.957122803 H -2.868988276-0.834600091 6.019474030 C -3.124436140 0.335018247 4.227894306 H -3.701869011 1.112148523 4.722177029 C -2.862318754 0.457615644 2.860152960 C -3.382258415 1.660793781 2.109777689 H -2.574625254 2.168253899 1.575544953 C -2.101604939-0.549711645 2.218665123 C -4.078579903-1.387582541 0.459456831 H -4.739990234-1.635861278-0.372431725 H -4.642790318-0.789988041 1.179959297 H -3.796797752-2.311743021 0.974016964 C -2.845195055-0.651612580-0.037342370 C -2.844640017-0.275325894-1.390271902 H -3.712195396-0.594855607-1.953347325 S10
C -1.942276120 0.532346010-2.103293657 C -2.394907475 0.962351859-3.488579750 H -2.561147690 2.043662548-3.525468111 H -3.324360609 0.461159229-3.763952017 H -1.636599422 0.734942973-4.242668152 C -0.120033562 2.025907516-2.375007391 C -0.509283900 3.353122711-2.087760210 C -1.563808084 3.655476570-1.050623894 H -1.266653895 3.277665377-0.067490019 C 0.105491146 4.398561954-2.783957958 H -0.185136601 5.421391010-2.558147669 C 1.076835155 4.148047447-3.749227762 H 1.546455860 4.971621037-4.279652596 C 1.436027527 2.834514380-4.034988403 H 2.184211731 2.629997015-4.796931267 C 0.847070158 1.755834937-3.364428520 C 1.266513228 0.349321723-3.700472593 H 0.415353090-0.309334338-3.893930435 C 4.854919910-3.032469034 0.105258800 C 3.734622002-3.812757969 0.403138101 H 3.858231306-4.802920341 0.834243059 C 4.676960468-1.765935063-0.449966609 H 5.538730621-1.150399685-0.693625212 C 2.453411102-3.330852747 0.147999212 H 1.584854245-3.944720745 0.366455913 C 3.394001961-1.277612329-0.703325450 H 3.258260250-0.291286111-1.133920431 C 2.264088154-2.049673080-0.397927731 C 0.266169369-2.442936420-1.592453718 C 0.903405726-2.844371796-2.786714077 H 1.909138799-2.495753765-2.992118597 S11
C -1.008780241-2.963495970-1.330358267 H -1.483682632-2.730122566-0.389180690 C 0.269640476-3.692793846-3.687804699 H 0.786399961-3.984026670-4.598710060 C -1.646036267-3.810347795-2.240675211 H -2.633076429-4.200078487-2.003783464 C -1.016543984-4.176407337-3.427086592 H 5.854217529-3.410408974 0.301125705 H -0.413294554-3.432091713 3.067378283 H -1.496826887-3.414340019 1.676477075 H -3.834953070 2.375390530 2.801952839 H -4.140656471 1.398523450 1.363144755 H -1.723404408 4.733768940-0.967525840 H -2.527911663 3.191256762-1.291272521 H 1.817761064-0.103217497-2.870498180 H 1.911012769 0.338213712-4.584583759 H -1.507821321-4.842664242-4.130534649 2 V 0.000000000 0.000000000 0.000000000 P 2.057490110 0.283660114 1.233149767 P 0.298362225 1.251308084 2.089112997 P 1.260253429 2.081138372 0.298612893 N -0.758794129 0.806371331-1.681728601 N -1.769695163-0.600581050 0.718564689 C -0.662587881-2.949072123 2.093379974 H 0.319973975-2.530200958 1.849998593 C -1.543058038-1.937207460 2.788429260 C -1.857195497-2.102669477 4.142267704 H -1.463183880-2.968275785 4.668829918 C -2.658818245-1.185063958 4.816740990 H -2.888434887-1.332353234 5.868136406 S12
C -3.165185452-0.079676732 4.136903286 H -3.790161610 0.640476823 4.658248425 C -2.882095814 0.123914048 2.781447649 C -3.420739174 1.335516095 2.060132027 H -2.602984905 1.957316041 1.678462625 C -2.064256191-0.812937379 2.114696980 C -3.806041002-1.945009351 0.286846131 H -4.382589817-2.306794882-0.566321969 H -4.480224609-1.397394180 0.952750921 H -3.436544895-2.805114031 0.852274716 C -2.661644697-1.061821580-0.175244644 C -2.627365828-0.742871761-1.542579412 H -3.400180340-1.207123041-2.142178774 C -1.811487436 0.174654976-2.228908777 C -2.192751884 0.458053797-3.671443939 H -2.407863855 1.520413876-3.819491386 H -3.073131561-0.118611798-3.959555626 H -1.372725725 0.206964567-4.351144791 C -0.116646983 1.820408583-2.482266903 C -0.588121593 3.147451639-2.385925293 C -1.735335946 3.494353056-1.467988968 H -1.513679266 3.201649904-0.436006039 C 0.037131611 4.138080597-3.149227381 H -0.317335397 5.162861824-3.075472832 C 1.103771091 3.826768875-3.990552187 H 1.580160856 4.605036259-4.579948902 C 1.555043221 2.513254642-4.074653625 H 2.383596420 2.266701460-4.734205246 C 0.960239708 1.487891436-3.329050303 C 1.497135997 0.080567606-3.438809156 H 0.707131743-0.673897088-3.467591286 S13
C 2.124899864-5.234760284-1.740164876 C 0.801859140-4.930204868-2.069690466 H 0.191148907-5.659588814-2.595906973 C 2.899759293-4.286254883-1.067750335 H 3.930627823-4.513753414-0.809014201 C 0.254737467-3.694204569-1.732446909 H -0.768829644-3.438433409-1.987651229 C 2.368265629-3.044117451-0.723136425 H 2.965070009-2.302106142-0.203209922 C 1.037320256-2.742373705-1.054351330 H 2.547877073-6.199023247-2.006691933 H -0.498687118-3.818511724 2.735921860 H -1.090205312-3.303135872 1.150455356 H -4.028874874 1.946892381 2.731919527 H -4.039316177 1.065023303 1.196584225 H -1.933890939 4.569175243-1.485285640 H -2.660861492 2.976516247-1.748523235 H 2.130157948-0.170811832-2.580121040 H 2.105697870-0.025830561-4.341240883 O 0.495260835-1.547353268-0.765239894 4 Mo 0.000000000 0.000000000 0.000000000 P 0.790622890 0.724874914 2.293251753 P 0.722483993 2.292839527 0.789443970 P 2.294381380 0.789774001 0.725583553 N 0.328859448 0.617472768-1.867512226 N -1.874337912 0.341383278 0.601972520 N 0.602312744-1.874951839 0.333869070 C 1.746698380-2.433379650 0.973390758 C 1.663826823-2.959839582 2.271806002 H 0.719372332-2.916327000 2.806689501 S14
C 2.976013422-2.476166964 0.301141322 H 3.034288883-2.074163437-0.705532551 C 2.791451931-3.503559351 2.885740042 H 2.715335369-3.892990351 3.897430182 C 4.101575375-3.021685123 0.918802917 H 5.047831059-3.042955160 0.385155350 C 4.014526367-3.537030220 2.212748289 H 4.892516136-3.956972361 2.695058584 C -2.879270554 0.076829597-0.438055336 H -3.365993500 0.999363303-0.782516062 H -2.420885324-0.394179434-1.316142201 H -3.656863213-0.602532864-0.062112387 C -0.445938498-2.868326664 0.058373839 H -0.081518471-3.634846449-0.639575481 H -0.787376940-3.369663954 0.973676682 H -1.324020147-2.393033743-0.395575076 C 0.062614970-0.413722217-2.882774830 H -0.386608094-1.304807663-2.427509546 H -0.634647131-0.037342034-3.643948793 H 0.983859837-0.735011280-3.387002707 C -2.427772284 0.975578427 1.753267646 C -2.501315117 0.287190557 2.971651793 C -2.921129227 2.287895918 1.683618307 C -3.046589375 0.902049184 4.099267483 H -2.116335392-0.726402402 3.024129868 C -3.464610100 2.899028301 2.812506914 H -2.851327658 2.832623959 0.746516347 C -3.529949188 2.208841801 4.024929047 H -3.088005543 0.358244389 5.039055347 H -3.827048540 3.921355009 2.747500658 H -3.948811054 2.687815666 4.905250549 S15
C 0.950672805 1.778229356-2.415311337 C 0.227434903 2.972724676-2.533970833 C 2.280036688 1.739019156-2.861610651 C 0.826092780 4.109740257-3.076868773 H -0.799964428 2.998986006-2.184102535 C 2.875272989 2.878151894-3.402380228 H 2.847130299 0.818123281-2.760066748 C 2.151403666 4.067182064-3.512291193 H 0.256146222 5.031651020-3.153529406 H 3.910736084 2.838914156-3.729248524 H 2.618615627 4.954788685-3.929069281 S16
References [1] Bruker (2009) SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. [2] Bruker (2009) SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. [3] An empirical correction for absorption anisotropy. R. Blessing, Acta Cryst. 1995, A51, 33-38. [4] Sir2004, A Program for Automatic Solution and Refinement of Crystal Structures. M. C. Burla, R. Caliandro, M. Carnalli, B. Carrozzini, G. L. Cascarano, L. De Caro, C. Giacovazzo, G. Polidori, R. Sagna. Vers. 1.0 (2004). [5] F. Neese, Diploma thesis, University of Konstanz (Konstanz, Germany) 1993. [6] Goodness-of-fit = [Σ[w(Fo 2 Fc 2 ) 2 ]/Nobservns Nparams)]1/2, all data. R1 = Σ( Fo Fc ) / Σ Fo. wr2 = [Σ[w(Fo 2 Fc 2 ) 2 ] / Σ [w(fo 2 ) 2 ]]1/2. S17