Supporting Information

Transcription

1 Supporting Informtion Wiley-VCH Weinheim, Germny

2 Supporting Informtion: An Iron Nitride Complex (nie ) Crol Vogel, Frnk W. Heinemnn, Jörg Sutter, Christin Anthon nd Krsten Meyer Deprtment of Chemistry nd Phrmcy Friedrich Alexnder University Erlngen-Nürnberg Egerlndstr. 1, Erlngen, Germny Fx: (+49) Emil: Generl Considertions: Synthesis nd Spectroscopy All ir- nd moisture-sensitive experiments were performed under dry nitrogen tmosphere using stndrd Schlenk techniques or n MBrun inert-gs glovebox contining n tmosphere of purified dinitrogen. Iron(II) chloride, nhydrous 99,9% ws purchsed from Aldrich nd used s received. Trimethylsilyl zide 97% nd sodium tetrphenylborte were purchsed from ACROS nd were used without further purifiction. Solvents were purified using two-column solidstte purifiction system (Glsscontour System, Irvine, CA) nd trnsferred to the glove box without exposure to ir. NMR solvents were obtined pckged under rgon nd stored over ctivted moleculr sieves nd sodium (where pproprite) prior to use. 1 H NMR spectr were recorded on JEOL 270 nd 400 MHz instruments operting t respective frequencies of nd MHz with probe temperture of 23 ºC. 13 C NMR spectr were recorded on JEOL 270 nd 400 MHz instruments operting t respective frequencies of MHz nd MHz with probe temperture of 23 ºC. Chemicl shifts were reported reltive to the pek for SiMe 4 using 1 H (residul) chemicl shifts of the solvent s secondry stndrd nd re reported in ppm. 15 N NMR dt were cquired on JEOL 400 MHz instrument, nd chemicl shifts were referenced to CH 3 NO 2 ( ppm reltive to liquid mmoni t 0 ppm). Electronic bsorption spectr were recorded from 300 to 2000 nm with UV-VIS-NIR- Spectrophotometer (Shimdzu UV-3600) in THF. All infrred spectr were recorded on Shimdzu IRPrestige-21 system in KBr pellets. Elementl nlysis results were obtined from the Anlyticl Lbortories t the Friedrich-Alexnder-University Erlngen-Nürnberg (Erlngen, Germny). 57 Fe Mößbuer spectr were recorded on WissEl Mößbuer spectrometer (MRG-500) t 77 K in constnt ccelertion mode. 57 Co/Rh ws used s the rdition source. WinNormos for Igor Pro softwre ws used for the quntittive evlution of the spectrl prmeters (lestsqures fitting to Lorentzin peks). The minimum experimentl line widths were 0.23 mms -1. The temperture of the smples ws controlled by n MBBC-HE0106 MÖSSBAUER He/N 2 cryostt within n ccurcy of ±0.3 K. Isomer shifts were determined reltive to α-iron t 298 K.

3 Computtion The electronic structure nd geometry of the iron(iv) nitride complex 4 xyl were investigted with Kohn-Shm DFT using the ORCA pckge. [1] For the geometry optimiztion the BP86 functionl [2-4] ws used together with the SV(P) bsis set [5] for the min group elements, nd the TZV(P) bsis for the iron centre. [6] The energy nd orbitls were clculted from the BP86 optimized structure using the B3LYP functionl. [7-9] References: [1] Neese, F. ORCA - An Ab Initio, Density Functionl nd Semiempiricl Progrm Pckge, version ; Institut für Physiklische und Theoretische Chemie, Universität Bonn, Germny, 2007 [2] Becke, A. D., Phys. Rev. A 1988, 38, [3] Perdew, J. P., Phys. Rev. B 1986, 33, [4] Perdew, J. P., Phys. Rev. B 1986, 34, [5] Schäfer, A.; Horn, H.; Ahlrichs, R., J. Chem. Phys. 1992, 97, [6] Schäfer, A.; Huber, C.; Ahlrichs, R., J. Chem. Phys. 1994, 100, [7] Becke, A. D., J. Chem. Phys. 1993, 98, [8] Lee, C. T.; Yng, W. T.; Prr, R. G., Phys. Rev. B: Condens. Mtter 1988, 37, [9] Stephens, P. J.; Devlin, F. J.; Chblowski, C. F.; Frisch, M. J., J. Phys. Chem. 1994, 98, Synthetic Detils: [(TIMEN mes )Fe(N 3 )]BPh 4 (3 mes ). Excess TMS-N 3 ws dded to solution of [(TIMEN mes )Fe]BPh 4 ( mg, 0.19 mmol) in 20 ml THF. The rection mixture ws stirred overnight, during which the red solution turned yellow. Hlf of the solvent ws removed nd ddition of 10 ml of diethyl ether to the solution induced precipittion of light yellow powder. The precipitte ws filtered, wshed with diethyl ether nd pentne, nd dried in vcuum (161.0 mg; yield: 79 %). Light yellow crystls suitble for X-ry diffrction nlysis were grown by diffusion of pentne into sturted solution of 3 mes in THF t room temperture. In the 1 H NMR, eleven signls re expected for the complex, nine re observed, two signls re likely brodened into the bseline. 1 H NMR (400 MHz, DMSO-d 6, 20 C): δ (s, 3H), (s, 3H), (s, 3H), (s, 3H), (s, 3H), 7.18 (m, 8H), 6.94 (m, 8H), 6.92 (m, 4H), 4.80 (s, 3H), 4.52 (s, 9H), 1.50 (s, 9H), (s, 9H). Elementl Anlysis (%) clcd for C 66 H 71 BFeN 10 : C 74.02, H 6.68, N Found: C 74.13, H 6.73, N [(TIMEN xyl )Fe(N 3 )]BPh 4 (3 xyl ) ws synthesized nlogous to the bove described procedure nd ws obtined in similr yield.

4 Figure S1. 1 H NMR spectrum of 3 mes (recorded in DMSO-d 6 ) BPh 4 # DMSO # # THF

5 Figure S2. IR spectrum of 3 mes (KBr pellet) Trnsmission / % Wvenumber / cm -1 Trnsmission / % Wvenumber / cm -1

6 [(TIMEN mes )Fe(N)]BPh 4 (4 mes ). A stirred solution of 3 mes (161.0 mg, 0.15 mmol) in 20 ml THF ws irrdited for 24h (Osrm XBO 150 W Xenon rc lmp) during which the yellow solution turned purple. The solution ws filtered through Celite, concentrted nd ddition of pentne to the solution induced precipittion of purple powder. The precipitte ws filtered, wshed with pentne, nd dried in vcuum (101.9 mg; yield: 65%). Purple crystls suitble for X-ry diffrction nlysis were grown by diffusion of diethyl ether into sturted solution of 4 mes in THF t room temperture. 1 H NMR (400 MHz, DMSO-d 6, 20 C): δ 7.59 (d, 3 J(H,H) = 1.8, 3H), 7.20 (d, 3 J(H,H) = 1.8, 3H), 7.16 (m, 8H), 6.86 (m, 8H), 6.75 (m, 4H), 6.61 (s, 3H), 6.60 (s, 3H), 4.06 (m, 3H), 3.10 (m, 3H), 2.68 (m, 3H), 2.26 (m, 3H), 2.13 (s, 9H), 1.61 (s, 9H), 0.92 (s, 9H). 13 C NMR (100 MHz, DMSO-d 6, 20 C): δ , , , , , , , , , , , 58.38, 50.56, 20.88, 17.36, Elementl nlysis (%) clcd for C 66 H 71 BFeN 8 : C 76.00, H 6.86, N Found: C 75.47, H 7.04, N [(TIMEN xyl )Fe(N)]BPh 4 (4 xyl ) ws synthesized nlogous to the bove described procedure nd ws obtined in similr yield.

7 Figure S3. 1 H NMR spectrum of 4 mes (recorded in DMSO-d 6 ) BPh 4 DMSO d d c b b b b

8 Figure S4. 13 C NMR spectrum of 4 mes (recorded in DMSO-d 6 ) b c BPh 4 DMSO N N N C Fe IV N b b c b c BPh 4 DMSO N N N C Fe IV N b b c

9 Figure S5. 15 N NMR spectrum of 15 N-lbeled isotopomer 4 mes (recorded in DMSO-d 6 )

10 Figure S6. IR spectrum of 4 mes (KBr pellet) Trnsmission / % Wvenumber / cm -1 Trnsmission / % Wvenumber / cm -1

11 Figure S7. IR spectrum of [(TIMEN mes )Fe( 14 N)]BPh 4, 4 mes (blck) nd 15 N-lbeled isotopomer [(TIMEN mes )Fe( 15 N)]BPh 4 (red, 50 % 15 N-lbeled t the terminl nitride) Trnsmission / % # FeN 14 FeN 15 # 1008 cm cm Wvenumber / cm -1

12 Figure S8. Electronic bsorption spectr of 3 mes (blck) nd 4 mes (mgent), recorded in THF Wvenumber / cm ε / M -1 cm Wvelength λ / nm 0

13 Crystllogrphic Supporting Informtion CCDC (for 3 mes 2.5 THF), CCDC (for 4 mes Et 2 O), CCDC (for 3 xyl MeCN), nd CCDC (for 4 xyl THF) contin the supplementry crystllogrphic dt for this pper. These dt cn be obtined free of chrge vi request/cif (or from Cmbridge Crystllogrphic Dt Centre, 12 Union Rod, Cmbridge, CB2 1EZ, UK (fx: ; e-mil: deposit@ccdc.cm.c.uk). X-ry Crystl Structure Determintion Detils: Ple-yellow needle-shped crystls of [(TIMEN mes )Fe(N 3 )]BPh THF (3 mes 2.5 THF), were grown by lyering THF solution of 3 mes with n-pentne, drk-violet prisms of [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O) were obtined by slow diffusion of Et 2 O into THF solution of 4 mes tht ws lyered with n-pentne, light-violet prisms of [(TIMEN xyl )Fe(N 3 )]BPh 4 MeCN (3 xyl MeCN) were obtined t r.t. by slow diffusion of Et 2 O into MeCN solution of 3 xyl, nd drk-violet pltes of [(TIMEN xyl )Fe(N)]BPh 4 THF (4 xyl THF) were grown t RT by lyering THF solution of 4 xyl with Et 2 O. Suitble single crystls were embedded in protective perfluoropolylkylether oil nd trnsferred to the cold nitrogen gs strem of the diffrctometer. Intensity dt of ll four crystls were collected t 100 K on Bruker-Nonius KppCCD diffrctometer using grphite monochromtized MoK α rdition. Dt were corrected for Lorentz nd polriztion effects, semiempiricl bsorption corrections were performed on the bsis of multiple scns using SADABS. [1] All structures were solved by direct methods nd refined by full-mtrix lest-squres procedures on F 2 using SHELXTL NT [2] All non-hydrogen toms were refined with nisotropic displcement prmeters. The hydrogen toms were plced in positions of optimized geometry, their isotropic displcement prmeters were tied to those of the corresponding crrier toms by fctor of either 1.2 or 1.5. Compound 1 crystllizes with totl of 2.5 molecules of THF with the hlf molecule being disordered on crystllogrphic inversion center. SIMU restrints were pplied for ll THF molecules nd dditionl SAME restrints were used for the disordered THF. The crystl structure of [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O) is subjected to disorder which ffects the ctionic iron complex exhibiting two different orienttions of the chelting lignd round the

14 centrl tom, the BPh 4 nion hving threefold disorder of the phenyl ring pointing towrds the ction s well s the Et 2 O solvent molecule tht is lso threefold disordered. This disorder gives rise to two pprent short contcts between disordered frgments of different prts nd orienttions, respectively, nmely the lignd of the ctionic complex nd the Et 2 O solvent molecules. ISOR nd SIMU restrints were used in the refinement of some of the ffected toms. The orienttionl disorder of the rotor-like rrnged lignd leds to two preferred orienttions tht re occupied by 67.6(2) nd 32.4(2) %, respectively, with few toms belonging to both orienttions; most importntly, the mine nitrogen, N1, the iron ion, Fe1, nd the nitride, N8, s well s N2, N4, nd C1. For the disordered phenyl ring (C61 C66) of the BPh 4 nion three preferred orienttions could be refined tht re occupied 36.0(5) % for toms C62 C66, 30.5(5) % for toms C62A C66A, nd 34.0(5) % for toms C62B C66B. The tretment of the threefold disorder of the Et 2 O solvent molecule resulted in site occupncies of 38.0(4) % for C101 C105, 32.0(4) % for C201 C205, nd 30.0(4)% for C301 C305. A number of restrints (SIMU, ISOR, nd SAME) ws pplied in the refinement of the disordered regions of the crystl structure of 4 mes Et 2 O. The THF molecule in the crystl structure of 4 xyl THF is disordered nd two lterntive positions were refined to give occupncies of 64.9(6) % for O100 C104 nd 35.1(6) for O110 C114. References: [1] SADABS 2.06, Bruker AXS, Inc., 2002, Mdison WI., U.S.A. [2] SHELXTL NT 6.12, Bruker AXS, Inc., 2002, Mdison WI., U.S.A. Tble S1 (next pge). Crystllogrphic dt, dt collection nd refinement detils of [(TIMEN mes )Fe(N 3 )]BPh THF (3 mes 2.5 THF), [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O), [(TIMEN xyl )Fe(N 3 )]BPh 4 MeCN (3 xyl MeCN) nd [(TIMEN xyl )Fe(N)]BPh 4 THF (4 xyl THF)

15 3 mes 2.5 THF 4 mes Et 2 O 3 xyl MeCN 4 xyl THF Empiricl formul C 76 H 91 BFeN 10 O 2.5 C 70 H 81 BFeN 8 O C 65 H 68 BFeN 11 C 67 H 73 BFeN 8 O Mol. weight Crystl size Temperture [K] Crystl system triclinic triclinic monoclinic triclinic Spce group P1 (no. 2) P1 (no. 2) P2 1 /n (no. 14) P1 (no. 2) [Å] (5) (2) (2) (9) b [Å] (2) (2) (1) (1) c [Å] (2) (3) (2) (2) α [ ] (10) (13) (7) β [ ] (6) (9) (1) (9) γ [ ] (7) (7) (7) V [Å 3 ] (6) (8) (10) (5) Z ρ [g/cm 3 ] (clc.) μ [mm -1 ] F (000) Abs. corr. SADABS SADABS SADABS SADABS T min ; T mx 0.861; ; ; ; Θ intervl [ ] 6.6 2Θ Θ Θ Θ 51.4 Coll. refl Indep. refl Obs. refl. F 0 4σ(F) No. ref. prm wr 2 (ll dt) R 1 (F 0 4σ(F)) GooF F Mx.; min. res. electr. density 0.623; ; ; ; 0.481

16 Tble S2. Selected bond distnces [Å] nd bond ngles [ ] with e.s.d. s in prentheses for [(TIMEN mes )Fe(N 3 )]BPh THF (3 mes 2.5 THF), [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O), [(TIMEN xyl )Fe(N 3 )]BPh 4 MeCN (3 xyl MeCN) nd [(TIMEN xyl )Fe(N)]BPh 4 THF (4 xyl THF) 3 mes 2.5 THF 4 mes mes xyl Et 2 O 4 Et 2 O 3 MeCN (mjor) # (minor) # 4 xyl THF Fe1 N (2) 3.120(2) 3.197(2) 2.984(3) Fe1 N (2) 1.526(2) 1.955(2) 1.527(3) Fe1 C (2) 1.987(3) 1.920(7) 2.099(2) 1.966(4) Fe1 C (3) 1.955(5) 1.982(10) 2.099(2) 1.952(4) Fe1 C (2) 1.946(4) 2.006(8) 2.104(2) 1.951(4) N8 N (3) (2) - N9 N (3) (2) - N2 C (3) 1.323(4) 1.391(7) 1.360(2) 1.362(4) N3 C (3) 1.382(4) 1.370(8) 1.364(2) 1.373(4) N4 C (3) 1.361(5) 1.268(10) 1.359(2) 1.376(4) N5 C (3) 1.373(5) 1.359(10) 1.367(2) 1.382(4) N6 C (3) 1.409(9) 1.31(2) 1.362(2) 1.369(4) N7 C (3) 1.374(4) 1.375(9) 1.367(2) 1.389(5) Fe1 N8 N (2) (2) - N8 N9 N (3) (2) - C3 Fe1 N (1) 115.1(2) 101.5(2) (7) 100.0(2) C8 Fe1 N (1) 101.4(2) 103.4(3) (7) 103.1(2) C13 Fe1 N (1) 103.8(2) 102.0(2) (7) 101.0(2) # In its crystl structure the ction 4 mes exhibits two different orienttions of the chelte lignd round the centrl tom with the mjor component being occupied by 67.6(2) nd the minor component by 32.4(2) % (see lso Figure S9 nd Figure S9b).

17 Grphicl Representtions Figure S9. Therml ellipsoid plot of the complex ction of [(TIMEN mes )Fe(N 3 )]BPh THF (3 mes 2.5 THF) with lbeling scheme (hydrogen toms omitted for clrity) Figure S9b. Therml ellipsoid plot of nion nd solvent molecules of [(TIMEN mes )Fe(N 3 )]BPh THF (3 mes 2.5 THF) with lbeling scheme (hydrogen toms omitted for clrity)

18 Figure S10. Therml ellipsoid plot of the complex ction (mjor component) of [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O) with lbeling scheme (hydrogen toms omitted for clrity) Figure S10b. Therml ellipsoid plot of the complex ction (minor component) of [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O) with lbeling scheme (hydrogen toms omitted for clrity)

19 Figure S10c. Therml ellipsoid plot of the disordered nion nd solvent molecules of [(TIMEN mes )Fe(N)]BPh 4 Et 2 O (4 mes Et 2 O) with lbeling scheme (hydrogen toms omitted for clrity)

20 Figure S11. Therml ellipsoid plot of the complex ction of [(TIMEN xyl )Fe(N 3 )]BPh 4 MeCN (3 xyl MeCN) with lbeling scheme (hydrogen toms omitted for clrity) Figure S11b. Therml ellipsoid plot of nion nd solvent molecules of [(TIMEN xyl )Fe(N 3 )]BPh 4 MeCN (3 xyl MeCN) with lbeling scheme (hydrogen toms omitted for clrity)

21 Figure S12. Therml ellipsoid plot of the complex ction of [(TIMEN xyl )Fe(N)]BPh 4 THF (4 xyl THF) with lbeling scheme (hydrogen toms omitted for clrity) Figure S12b. Therml ellipsoid plot of nion nd disordered solvent molecule of [(TIMEN xyl )Fe(N)]BPh 4 THF (4 xyl THF) with lbeling scheme (hydrogen toms omitted for clrity)