Supporting Information

Transcription

1 Supporting Information Insertion into dihydrogen employing the nitrogen centre of a borylnitrene olger F. Bettinger, a,b, * Matthias Filthaus, a and Patrik Neuhaus a a Lehrstuhl für Organische hemie II, Ruhr-Universität Bochum, Universitätsstrasse 15, 4478 Bochum, Germany b Instiut für Organische hemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 7276 Tübingen, Germany holger.bettinger@uni-tuebingen.de I. Experimental and omputational Details The azide 2 was synthesized as described previously. 1 Matrix experiments. Matrix experiments were carried out using standard techniques 2 with and Sumitomo closed-cycle helium cryostats. Matrices were produced by codeposition of a large excess of deuterium or mixtures of deuterium with neon (Messer-Griesheim, %) and hydrogen (UAR, ultra high purity) with neon and the azide 2 held at by means of an ice bath on top of a cold si or quartz window. During the deposition the temperature of the window was maintained at 3 K. IR spectra were recorded with Bruker IFS 66/S FTIR spectrometer with a resolution of.5 cm 1 in the range of 4 4 cm 1. EPR spectra were recorded with a Bruker Elexsys E5 spectrometer. The computer simulation of the EPR spectrum of 3 was performed by using the XSophe computer simulation software suite (version.4), 3 developed by the entre for Magnetic Resonance and Department of Mathematics, University of Queensland, Brisbane (Australia) and Bruker Analytik Gmb, S1

2 Rheinstetten (Germany). The simulation was performed by using a matrix diagonalization method for S = 1 and setting the parameters ν = Gz, g = 2.23, D/hc = 1.58 cm 1 and E/hc =.3 cm 1. Irradiations were carried out with a Gräntzel low pressure mercury lamp (254 nm) and an Osram BO-5-W/2 high pressure mercury lamp in an Oriel housing with quartz optics, a dichroic mirror (42 68 nm), and a Schott cutoff filter (55 nm). omputations. Geometry of 3 was optimized and vibrational frequencies were obtained using the B3LYP 4 functional in conjunction with the G** basis set as included in the Gaussian 3 program. 5 The ASSF computation of the transition state for insertion considered the lowest energy singlet state of boryl nitrene 1, i.e., 1 A 1. The active space was modified based on the 12 by 11 space (all 12 π electrons distributed over 1 π and one empty N(σ) orbital) employed in our previous investigation. 6 orrelation of the two π lone pairs of oxygen atoms is not essential as indicated by their high occupations numbers of In view of the reduced symmetry from 2v for 1 to 1 for the TS of 2 addition, these two π lone pairs of oxygen atoms were not included into the active space thus reducing it to 8 π electrons and 8 π orbitals. In addition, the σ/σ* orbitals and the electron pair of the molecule as well as the N(sp) lone pair and the vacant N(p) were included resulting in a 12 by 12 active space, (12,12)-ASSF. In view of the large active space the 6-31G* basis set was used for the ASSF calculations. armonic vibrational frequencies were computed analytically and the intrinsic reaction coordinate was computed using the default values of the GAMESS program. 7 Energies were refined by single state multiconfiguration perturbation theory (MRMP2) single point computations with identical active spaces again using the 6-31G* basis set. The ASSF and MRMP2 calculations were performed with GAMESS. 7 S2

3 As we have observed earlier 6 that the multiconfiguration nature of borylnitrene 1 is handled well by coupled cluster theory with singles, double, and a perturbative estimate of triple excitations [SD(T)] 8 in conjunction with the correlation consistent triple-ζ basis set, 9 this method has also been used for single point computations employing the (12,12)- ASSF/6-31G* geometries. The MOLPRO 1 program was employed for all SD(T) runs. S3

4 II. artesian oordinates and Energies of 2-amino-1,3,2-benzodioxaborole (3) as computed at the B3LYP/6-311+G** level of theory. Method: B3LYP/6-311+G** Stoichiometry 66BNO2 Framework group 2V[2(BN),SGV(66O2)] Deg. of freedom Full point group 15 2V NOp 4 Largest Abelian subgroup 2V NOp 4 Largest concise Abelian subgroup 2 NOp Standard orientation: enter Number Atomic Number Atomic Type oordinates (Angstroms) X Y Z Rotational constants (GZ): SF Done: E(RB+F-LYP) = onvg =.4284D-8 A.U. after 1 cycles -V/T = 2.39 S**2 =. Item Value Threshold onverged? Maximum Force YES RMS Force Maximum Displacement YES YES RMS Displacement.11.4 YES Predicted change in Energy= D-9 S4

5 III. artesian oordinates computed at the (12,12)-ASSF/6-31G* level of theory. 1) Transition state for insertion of 1 into the bond TE POINT GROUP OF TE MOLEULE IS 1 TE ORDER OF TE PRINIPAL AXIS IS ATOM ATOMI ARGE X OORDINATES (BOR) Y Z O B N O FINAL MSF ENERGY IS AFTER 2 ITERATIONS TOTAL MRPT2, E(MP2) T + 1ST + 2ND ORDER ENERGY = SD(T) F-SF ) Endpoint of the IR calculation forward side TE POINT GROUP OF TE MOLEULE IS 1 TE ORDER OF TE PRINIPAL AXIS IS ATOM ATOMI ARGE X OORDINATES (BOR) Y Z O B N O FINAL MSF ENERGY IS AFTER 2 ITERATIONS TOTAL MRPT2, E(MP2) T + 1ST + 2ND ORDER ENERGY = SD(T) F-SF ) Endpoint of the IR calculation reverse side TE POINT GROUP OF TE MOLEULE IS 1 TE ORDER OF TE PRINIPAL AXIS IS S5

6 ATOM ATOMI OORDINATES (BOR) ARGE X Y Z O B N O FINAL MSF ENERGY IS AFTER 2 ITERATIONS TOTAL MRPT2, E(MP2) T + 1ST + 2ND ORDER ENERGY = SD(T) F-SF S6

7 IV. Experimental and omputed Vibrational Data for 3, atbnd 2. Table S1. omputed and Experimental Vibrational Data of 3. B3LYP/6-311+G** [a] 3 at 3 K in D 2 11 B Isotopomer B Isotopomer B/ 1 B B B B/ 1 B rel. Int. number [b] sym ω/cm 1 rel. Int. ω/cm 1 rel. Int. ~ ν /cm 1 ~ ν /cm 1 42 A B A B B w 37 A m 36 A B [e] vw 34 A s A [c] [d] vs B A s 3 B B [e].986 m 28 A s 27 A A B w 24 B A w 22 A B [e] vw 2 A m 19 B S7

8 18 A A w 16 B m 15 A B B w 12 A B A A B B [d] vw 6 A B B A B B [a] These signals increase during λ 55 nm irradiation. [b] Mode numbers taken from the computed spectrum. [c] Absolute intensity: km mol 1. [d] Absolute intensity: km mol 1. [e] Tentative assignment. S8

9 Table S2. omparison of the bands disappearing during λ 55 nm irradiation in solid D 2 at 3 K with those assigned previously to 1 isolated in solid argon at 1K. D 2, ~ ν /cm 1 Ar, ~ ν /cm 1 [b] rel. Int. [b] , , , , [a] Bands disappear during λ 55 nm irradiation. [b] Taken from Reference 6. V. ESR Spectrum of 1 in solid deuterium at 4 K. Figure. ESR spectra obtained during the irradiation of azide 2 isolated in a deuterium matrix at 4 K. Trace a) after 254-nm irradiation; trace b) after subsequent >55-nm irradiation. S9

10 References 1 Fraenk, W.; abereder, T.; Klapötke, T. M.; Nöth,.; Polborn, K. J. hem. Soc., Dalton Trans. 1999, I. R. Dunkin, Matrix Isolation Techniques: A Practical Approach, Oxford University Press, Oxford, Griffin, M.; Muys, A.; Noble,.; Wang, D.; Eldershaw,.; Gates, K. E.; Burrage, K.; anson, G. R. Mol. Phys. Rep. 1999, 26, a) A. D. Becke, J. hem. Phys. 1993, 98, 5648 ;b) P. J. Stephens, F. J. Devlin,. F. habalowski, M. J. Frisch, J. Phys. hem. 1994, 98, 11623; c). Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, M. J. Frisch, G. W. Trucks,. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. heeseman, J. J. A. Montgomery, T. Vreven, K. N. Kudin, J.. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. ossi, G. Scalmani, N. Rega, G. A. Petersson,. Nakatsuji, M. ada, M. Ehara, K. Toyota, R. Fukuda, J. asegawa, M. Ishida, T. Nakajima, Y. onda, O. Kitao,. Nakai, M. Klene, X. Li, J. E. Knox,. P. ratchian, J. B. ross,. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. ammi,. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M.. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. ui, A. G. Baboul, S. lifford, J. ioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham,. Y. Peng, A. Nanayakkara, M. hallacombe, P. M. W. Gill, B. Johnson, W. hen, M. W. Wong,. Gonzalez, J. A. Pople, Gaussian 3, Revision B.4, Gaussian, Inc., Pittsburgh PA, F. Bettinger,. Bornemann, J. Am. hem. Soc. 26, 128, M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J.. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, J. omput. hem. 1993, 14, a) K. Raghavachari, G. W. Trucks, J. A. Pople, M. ead-gordon, hem. Phys. Lett. 1989, 157, 479; b). ampel, K. Peterson,.-J. Werner, hem. Phys. Lett. 1992, 19, 1; c) J. D. Watts, J. Gauss, R. J. Bartlett, J. hem. Phys. 1993, 98, 8718; d) P. J. Knowles,. ampel,.-j. Werner, J. hem. Phys. 1993, 99, T.. Dunning, J.hem.Phys. 1989, 9, 17. S1

11 1 MOLPRO, a package of ab initio programs designed by.-j. Werner and P. J. Knowles, version 22.1, R. D. Amos, A. Bernhardsson, A. Berning, P. elani, D. L. ooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert,. ampel, G. etzer, P. J. Knowles, T. Korona, R. Lindh, A. W. Lloyd, S. J. McNicholas, F. R. Manby, W. Meyer, M. E. Mura, A. Nicklass, P. Palmieri, R. Pitzer, G. Rauhut, M. Schütz, U. Schumann,. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, and.-j. Werner. S11