Dynamic Exchange in Intramolecular Lewis Pairs with Multiple Lewis-acidic Functions Leif A. Körte, Sebastian Blomeyer, Jan-Hendrik Peters, Andreas Mix, Beate Neumann, Hans-Georg Stammler and Norbert W. Mitzel Lehrstuhl für Anorganische Chemie und Strukturchemie und Centrum für Molekulare Materialien CM 2, Fakultät für Chemie, Universität Bielefeld, Universitätstraße 25, 33615 Bielefeld (Germany) E-mail: mitzel@uni-bielefeld.de N,N-Diallyl-N-methylamine (2) Additional Spectra Figure S1. 1 H NMR spectrum (500 MHz, CDCl 3 ) of N,N-diallyl-N-methylamine (2). Figure S2. 13 C{ 1 H} NMR spectrum (126 MHz, CDCl 3 ) of N,N-diallyl-N-methylamine (2).
Diallylmethylphosphane (4) Figure S3. 1 H NMR spectrum (300 MHz, C 6 D 6 ) of diallylmethylphosphane (4). Figure S4. 13 C{ 1 H} NMR spectrum (76 MHz, C 6 D 6 ) of diallylmethylphosphane (4). Figure S5. 31 P{ 1 H} NMR spectrum (121 MHz, C 6 D 6 ) of diallylmethylphosphane (4).
Me 2 N-CH 2 -CH 2 -CH 2 -BBN (6) Figure S6. 1 H NMR spectrum (500 MHz, Tol-d 8, 373 K) of Me 2 N-CH 2 -CH 2 -CH 2 -BBN (6). Figure S7. 11 B NMR spectrum (192 MHz, Tol-d 8, 383 K) of Me 2 N-CH 2 -CH 2 -CH 2 -BBN (6). Figure S8. 13 C{ 1 H} NMR spectrum (126 MHz, Tol-d 8, 373 K) of Me 2 N-CH 2 -CH 2 -CH 2 -BBN (6).
MeN-(CH 2 -CH 2 -CH 2 -BBN) 2 (7) For 11 B NMR spectra see main paper. Figure S9. 1 H NMR spectrum (600 MHz, Tol-d 8, 363 K) of MeN(CH 2 -CH 2 -CH 2 -BBN) 2 (7). Due to fast exchange only one set of signals can be observed for both (CH 2 ) 3 BBN side arms. During the measurement decomposition at high temperature, probably by dehydroboration occurs. Therefore, some signals of decomposition products can be observed. Figure S10. 13 C{ 1 H} NMR spectrum (126 MHz, Tol-d 8, 373 K) of MeN(CH 2 -CH 2 -CH 2 -BBN) 2 (7). Due to fast exchange only one set of signals can be observed for both (CH 2 ) 3 BBN side arms. During the measurement decomposition at high temperature, probably by dehydroboration occurs. Therefore, many signals of decomposition products can be observed. Figure S11. 13 C{ 1 H} NMR spectrum (126 MHz, C 6 D 6, 298 K) of MeN(CH 2 -CH 2 -CH 2 -BBN) 2 (7). Due to dynamic exchange at ambient temperature the resonances are broadened and not all expected resonances can be observed.
N-(CH 2 -CH 2 -CH 2 -BBN) 3 (9) For 11 B NMR see VT-NMR spectra in the main paper. Figure S12. 1 H NMR spectrum (300 MHz, C 6 D 6, 298 K) of N(CH 2 -CH 2 -CH 2 -BBN) 3 (9). Figure S13. 13 C{ 1 H} NMR spectrum (76 MHz, C 6 D 6, 298 K) of N(CH 2 -CH 2 -CH 2 -BBN) 3 (9). MeP-(CH 2 -CH 2 -CH 2 -BBN) 2 (10) For 11 B NMR see VT-NMR spectra in the main paper. Figure S14. 1 H NMR spectrum (500 MHz, C 6 D 6, 298 K) of MeP(CH 2 -CH 2 -CH 2 -BBN) 2 (10).
Figure S15. 1 H NMR spectrum (500 MHz, Tol-d 8, 393 K) of MeP(CH 2 -CH 2 -CH 2 -BBN) 2 (10). Due to a severe overlap of the resonances no assignment was possible, even when measured at elevated temperature. Figure S16. 13 C{ 1 H} DEPT-135 NMR spectrum (76 MHz, Tol-d 8, 393 K) of MeP(CH 2 -CH 2 -CH 2 -BBN) 2 (10). Due to a severe overlap of the resonances in the 1 H NMR spectra as well as line broadening due to the exchange of the boron Lewis acids no assignment of all resonances was possible. Figure S17. 31 P{ 1 H} NMR spectrum (202 MHz, C 6 D 6, 298 K) of MeP(CH 2 -CH 2 -CH 2 -BBN) 2 (10).
Crystallographic data: Table S1. Crystallographic data of compounds 6, 7 and 9. Empirical formula 6 7 9 C 13 H 26 BN C 23 H 43 B 2 N C 33 H 60 B 3 N M r 207.16 355.20 503.25 F(000) 464 792 560 Crystal system monoclinic monoclinic triclinic Space group P2 1 /n P2 1 /c P1 a [Å] 9.3027(2) 15.1625(5) 8.4657(7) b [Å] 12.2196(2) 11.1717(2) 13.074(2) c [Å] 11.0832(2) 13.8554(4) 14.283(2) α [ ] 90 90 75.75(1) β [ ] 102.641(2) 116.224(4) 80.154(8) γ [ ] 90 90 82.275(9) V [Å 3 ] 1229.34(4) 2105.4(1) 1502.6(3) Z 4 4 2 ρ calcd. [g cm 3 ] 1.119 1.121 1.112 μ [mm 1 ] 0.456 0.447 0.440 2θ max [ ] 152.7 144.2 144.3 Index range h 11 h 11 18 h 18, 10 h 10, Index range k 15 k 15 13 k 13 16 k 16 Index range l 13 l 13 17 l 17 16 l 17 Refl. collect. 20960 32791 16286 Indep. refl. 2565 4153 6431 R int 0.0264 0.0495 0.0464 Observed refl., I>2σ(I) 2336 3301 4973 Parameters 241 249 363 R 1, I>2σ(I) 0.0323 0.0406 0.0476 wr 2, I>2σ(I) 0.0866 0.0980 0.1266 R 1 (all data) 0.0355 0.0553 0.0613 wr 2 (all data) 0.0893 0.1076 0.1323 GoF 1.059 1.026 1.056 ρ max/min [e Å 3 ] 0.33/ 0.15 0.26/ 0.18 0.25/ 0.28 CCDC-No. 1441278 1441279 1441280
Computational details E(PW6B95-D3BJ(abc)/def2-TZVP//PBEh-3c) + δ thermo(pbeh-3c) + δ solvation(pw6b95-d3bj(abc)/def2-tzvp/cosmo(toluene)//pbeh-3c) closed-7 Figure S18. Calculated structure of closed-7. 2647825.92 kj mol 1 1478.63 kj mol 1 7.4721219 kj mol 1 2646418.59 kj mol 1
open-7 Figure S19. Calculated structure of open-7. 2647889.75 kj mol 1 1447.95 kj mol 1 3.97 kj mol 1 2646381.93 kj mol 1 TS-7 Figure S20. Calculated structure of TS-7. ṽ imag = 2647811.44 kj mol 1 1462.04 kj mol 1 3.53 kj mol 1 2646352.94 kj mol 1 192.74 cm 1
closed-10 Figure S21. Calculated structure of closed-10. 3401002.71 kj mol 1 1407.35 kj mol 1 8.48 kj mol 1 3399603.84 kj mol 1 open-10 Figure S22. Calculated structure of open-10. 3400934.93 kj mol 1 1391.50 kj mol 1 6.78 kj mol 1 3399558.26 kj mol 1
TS-10 Figure S23. Calculated structure of TS-10. ṽ imag = 3400835.50 kj mol 1 1414.41 kj mol 1 4.88 kj mol 1 3399425.97 kj mol 1 393.60 cm 1