Paramagnetic Aluminum -Diketiminate

Transcription

1 Supporting Informtion for Prmgnetic Aluminum -Diketiminte by Jni Moilnen, Jvier Boru Grci, Rolnd Roesler, nd Heikki M. Tuononen*

2 1. Experimentl detils All rections nd mnipultions were performed under n rgon tmosphere by using Schlenk techniques or n inert tmosphere glove box. Compounds MeAlCl 2 (1 M in hexnes, Aldrich) nd n-buli (1.6 M in hexnes, Aldrich) were used s received. B(C 6 H 5 ) 3 nd B(C 6 F 5 ) 3 (Aldrich) were dried with HMe 2 SiCl nd sublimed before use. CoCp * 2 nd CoCp 2 (Aldrich) were sublimed before use. Compound 7 ws prepred ccording to literture procedure (Eur. J. Org. Chem., 2004, 4319). All solvents were dried nd deoxygented prior to use. NMR spectr were recorded on Bruker Avnce 400 MHZ or Bruker Avnce II 300 MHZ spectrometer. 1 H nd 13 C spectr were referenced to the residul solvent signl nd the chemicl shifts re reported reltive to (CH 3 ) 4 Si. Solutions of BF 3 Et 2 O in C 6 D 6 nd net C 6 F 6 were used s internl references in 11 B nd 19 F mesurements, respectively. The EPR spectrum of 4j ws recorded using n X-bnd Bruker EMX10/12 spectrometer. Elementl nlyses were performed by Anlyticl Services t the Deprtment of Chemistry, University of Clgry. Although the clculted nd experimentl dt for the elementl nlysis of both 9 nd 9b devite slightly ( %), the purity of the compounds is clerly shown by NMR spectroscopy (see below) s there there re no 11 B- or 19 F-contining impurities present in the smple. Consequently, we ddress the minor errors in elementl nlysis to smll mount of H-grese present in the products. 8: A solution of 7 (681 mg, 4.0 mmol) in THF (10 ml) ws cooled to -78 C nd n- BuLi (2.5 ml of 1.6 M solution in hexne, 4.0 mmol) ws dded by syringe. The solution ws stirred for 1 h t -78 C nd then wrmed to -40 C. MeAlCl 2 (2.0 ml of 1 M solution in hexne, 2.0 mmol) ws dded by syringe nd the solution ws llowed to wrm to mbient temperture over 1 h, fter which it ws wrmed to 45 C nd stirred for dditionl 45 min. The hot solution ws filtered nd the solvents evported under vcuum. The residue ws dissolved in CH 2 Cl 2 (10 ml), filtered nd the solvent ws evported under vcuum. The solid residue ws wshed with hexne (2 x 10 ml) to fford 8 s n ornge powder (430 mg, 57%). Crystlliztion from CH 2 Cl 2 yielded ornge single crystls suitble for X-ry nlysis (see below). 1 H NMR ( MHz, THF-d8, S1

3 300 K) (ppm) = 7.29 (d, J = 5.20 Hz, 4H), = 7.01 (m, 4H), = 6.67 (d, J = 8.81 Hz, 4H), = 6.14 (t, J = 6.00 Hz, 4H), = 5.22 (s, 2H), = (S, 3H). 13 C NMR ( MHz, THF-d8, 300 K) (ppm) = , = , = , = , = , = 90.77, = Elementl nlysis clcd. (%) for C 23 H 21 AlN 4 : C 72.60, H 5.56, N 14.73; found: C 72.39, H 5.70, N : 8 (300 mg, 0.79 mmol) ws dissolved in CH 2 Cl 2 (5 ml) nd solution of B(C 6 F 5 ) 3 (404 mg, 0.79 mmol) in CH 2 Cl 2 (5 ml) ws dded by syringe t mbient temperture. The solution ws stirred for 2 h t mbient temperture nd the solvent ws evported under vcuum. The residue ws wshed with hexne (1x 10 ml) to fford 9 s n ornge powder (580 mg, 82 %). 1 H NMR ( MHz, CD 2 Cl 2, 300 K) (ppm) = 7.40 (m, 4H), = 7.31 (d, J = 6.40 Hz, 4H), = 7.09 (d, J = 8.81 Hz, 4H), = 6.55 (td, J = 6.80, 1.2 Hz, 4H), = 5.63 (s, 2H), = 0.46 (S, 3H). 13 C (prtil) NMR ( MHz, CD 2 Cl 2, 300 K) (ppm) = , = , = , = , = , = , = , = , = , = B NMR ( MHz, CD 2 Cl 2, 300 K) (ppm) = F NMR ( MHz, CD 2 Cl 2, 300 K) (ppm) = , = , = Elementl nlysis clcd. (%) for C 41 H 21 AlBF 15 N 4 : C 55.18, H 2.37, N 6.28; found: C 53.71, H 3.12, N b: 8 (135 mg, 0.35 mmol) ws dissolved in CH 2 Cl 2 (5 ml) nd solution of B(C 6 H 5 ) 3 (86 mg, 0.35 mmol) in CH 2 Cl 2 (5 ml) ws dded by syringe t mbient temperture. The solution ws stirred for 2 h t mbient temperture nd the solvent ws evported under vcuum. The residue ws wshed with hexne (1x 10 ml) to fford 9b s n ornge powder (135 mg, 61 %). 1 H NMR ( MHz, CD 2 Cl 2, 293 K) (ppm) = (severl m, 31H), = 5.33 (s, 2H), = 0.27 (q, J = 4.08 Hz, 3H. 13 C (prtil) NMR (75.48 MHz, CD 2 Cl 2, 293 K) (ppm) = , = , = , = , = , = , = , = , = , = B NMR (96.29 MHz, CD 2 Cl 2, 294 K) (ppm) = Elementl nlysis clcd. (%) for C 41 H 42 AlBN 4 : C 78.34, H 6.73, N 8.91; found: C 78.67, H 5.83, N j: Method : 9 (200 mg, 0.22 mmol) ws dissolved in CH 2 Cl 2 (10 ml) nd solution of CoCp * 2 (74 mg, 0.22 mmol) in CH 2 Cl 2 (5 ml) ws dded by syringe t mbient temperture. The solution ws stirred for overnight t mbient temperture fter S2

4 which the solvent ws evported under vcuum to fford gryish brown solid residue, which ws nlyzed by EPR spectroscopy to contin 4j. Method b: 9 (5 mg, mmol) nd piece of potssium metl ws dded in toluene (2 ml) nd trnsferred into n EPR tube. The EPR tube ws sonicted for 15 min nd the drk red solution ws nlyzed by EPR spectroscopy to contin 4j. Method c: 9b (80 mg, 0.13 mmol) ws dissolved in CH 2 Cl 2 (10 ml) nd solution of CoCp 2 (45 mg, 0.13 mmol) in CH 2 Cl 2 (5 ml) ws dded by syringe t mbient temperture. The solution ws stirred for overnight t mbient temperture fter which the solvent ws evported under vcuum to fford gryish brown solid residue. Crystlliztion from CH 2 Cl 2 :toluene (50:50) mixture fforded the cobltocenium slt of trisphenylmethylborte s yellow crystls suitble for X-ry nlysis (see below). S3

5 2. Crystllogrphic dt Crystllogrphic dt of 8: Identifiction code shelxl Empiricl formul C23 H21 Al N4 Formul weight Temperture 173(2) K Wvelength Å Crystl system Monoclinic Spce group P 21/c Unit cell dimensions = (9) Å = 90. b = (4) Å = (2). c = (10) Å = 90. Volume (2) Å 3 Z 4 Density (clculted) Mg/m 3 Absorption coefficient mm -1 F(000) 800 Crystl size 0.24 x 0.04 x 0.04 mm 3 Thet rnge for dt collection 2.96 to Index rnges -15<=h<=15, -11<=k<=11, -18<=l<=18 Reflections collected 5851 Independent reflections 3399 [R(int) = ] Completeness to thet = % Absorption correction Semi-empiricl from equivlents Mx. nd min. trnsmission nd Refinement method Full-mtrix lest-squres on F 2 Dt / restrints / prmeters 3399 / 0 / 261 Goodness-of-fit on F Finl R indices [I>2sigm(I)] R1 = , wr2 = R indices (ll dt) R1 = , wr2 = Lrgest diff. pek nd hole nd e.å -3 Crystllogrphic dt of [CoCp 2 ][Ph 3 BMe]: Identifiction code shelxl Empiricl formul C29 H28 B Co S4

6 Formul weight Temperture 123(2) K Wvelength Å Crystl system orthorhombic Spce group Pmn 21 Unit cell dimensions = (3) Å = 90. b = (2) Å = 90. c = (3) Å = 90. Volume (8) Å 3 Z 4 Density (clculted) Mg/m 3 Absorption coefficient mm -1 F(000) 936 Crystl size 0.15 x 0.2 x 0.3 mm 3 Thet rnge for dt collection 2.73 to Index rnges 0<=h<=13, -15<=k<=0, -18<=l<=18 Reflections collected 4153 Independent reflections 4153 [R(int) = ] Completeness to thet = % Refinement method Full-mtrix lest-squres on F 2 Dt / restrints / prmeters 4153 / 1 / 302 Goodness-of-fit on F Finl R indices [I>2sigm(I)] R1 = , wr2 = R indices (ll dt) R1 = , wr2 = Absolute structure prmeter 0.74(2) Lrgest diff. pek nd hole nd e.å -3 S5

7 Figure S1. The crystl structure of [CoCp 2 ][Ph 3 BMe] (therml ellipsoids drwn t 30% probbility; hydrogen toms omitted for clrity). S6

8 3. Spectroscopic dt Figure S2. The 11 B NMR spectrum of 9 in CD 2 Cl 2. S7

9 Figure S3. The 19 F NMR spectrum of 9 in CD 2 Cl 2. S8

10 Figure S4. The 11 B NMR spectrum of 9b in CD 2 Cl 2. S9

11 Figure S5. EPR-spectrum of 4j s obtined from powder smple (T = 295 K, mod.mp. = 1.0 G). S10

12 4. Computtionl detils The structures of rdicls 3-6 were optimized by using density functionl theory nd the PBE1PBE hybrid functionl. 1 The clcultions used the Ahlrichs def2-tzvp bsis sets; 2 for indium, the corresponding effective core potentil bsis set ws used. Frequency nlyses were performed for optimized geometries to ensure tht they correspond to stble minim on the potentil energy hypersurfce. Clculted spin densities were prtitioned to contributions from individul toms with the help of Mulliken popultion nlysis All clcultions were done with the Turbomole 6.3 nd Gussin 09 progrm pckges () J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1997, 78, 1396; (b) J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865; (c) J. P. Perdew, M. Ernzerhof, K. Burke, J. Chem. Phys., 1996, 105, 9982; (d) C. Admo, V. Brone, J. Chem. Phys., 1999, 10, () F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, 3297; (b) F. Weigend, M. Häser, H. Ptzelt, R. Ahlrichs, Chem. Phys. Lett., 1998, 294, 143. () TURBOMOLE V , development of University of Krlsruhe nd Forschungszentrum Krlsruhe GmbH, , TURBOMOLE GmbH, since 2007; vilble from (b) Gussin 09, Revision A.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseri, M. A. Robb, J. R. Cheesemn, G. Sclmni, V. Brone, B. Mennucci, G. A. Petersson, H. Nktsuji, M. Cricto, X. Li, H. P. Hrtchin, A. F. Izmylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hd, M. Ehr, K. Toyot, R. Fukud, J. Hsegw, M. Ishid, T. Nkjim, Y. Hond, O. Kito, H. Nki, T. Vreven, J. A. Montgomery, Jr., J. E. Perlt, F. Ogliro, M. Berprk, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Stroverov, R. Kobyshi, J. Normnd, K. Rghvchri, A. Rendell, J. C. Burnt, S. S. Iyengr, J. Tomsi, M. Cossi, N. Reg, J. M. Millm, M. Klene, J. E. Knox, J. B. Cross, V. Bkken, C. Admo, J. Jrmillo, R. Gomperts, R. E. Strtmnn, O. Yzyev, A. J. Austin, R. Cmmi, C. Pomelli, J. W. Ochterski, R. L. Mrtin, K. Morokum, V. G. Zkrzewski, G. A. Voth, P. Slvdor, J. J. Dnnenberg, S. S11

13 Dpprich, A. D. Dniels, Ö. Frks, J. B. Foresmn, J. V. Ortiz, J. Cioslowski, nd D. J. Fox, Gussin, Inc., Wllingford CT, S12

14 5. Computtionl dt Figure S6. The SOMOs (left) nd spin densities (right) of 4-k. Colour code: ornge = positive spin density, green = negtive spin density. S13

15 Tbel S1. Moleculr point groups of 3-6. Point group Point group Point group Point group 3 S 4 4 D 2d 5 D 2d 6 C 2 3b S 4 4b D 2d 5b D 2d 6b C 2v 3c D 2 4c D 2 5c C 2 3d D 2d 4d D 2d 5d D 2d 6d C 1 3e S 4 4e S 4 5e C 2 3f D 2 4f D 2 5f C 2 3g S 4 4g S 4 5g C 2 3h 3i C 2 C s 4h C 2 5h C 2 4i S 4 5i D 2 6i D 2 3j D 2d 4j D 2d 5j D 2d 6j D 2d 3k C 2 4k C 2 5k C 2 6k C 2 ) Spin density loclized on one lignd only. 6c 6e 6f 6g 6h C 2 C 1 C 2 C 2 C 2 S14

16 Tble S2. Mulliken spin densities of 3-6 t the PBE1PBE/def2-TZVP level of theory. N 1 /N 5 C 2 /C 4 C 3 B N 1 /N 5 C 2 /C 4 C 3 G b b c c / / / d d e e / / / f f / / / g g / / / / / / h / / / h i / / / i j j k k S15

17 Tble S2. Continued. N 1 /N 5 C 2 /C 4 C 3 Al N 1 /N 5 C 2 /C 4 C 3 In / / / b b / / / c c / / / d d / / / e e / / / f f / / / g g / / / h / / / / / / h i i j j k k S16