Supporting Information

Transcription

1 Supporting Information

2 Supplementary Materials Isolation and characterisation of well-defined silicasupported azametallacyclopentane: key intermediate in catalytic hydroaminoalkylation reactions Bilel Hamzaoui, Jérémie D. A. Pelletier, Mohamad El Eter, Yin Chen, Edy Abou- Hamad, and Jean-Marie Basset, * Corresponding Authors: Jeanmarie.basset@kaust.edu.sa King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering, KAUST Catalysis Center, Thuwal , Saudi Arabia. 1

3 Supporting Information: Table of Contents Contents 1. General Procedures Elemental analysis Solid State Nuclear Magnetic Resonance Spectra Regeneration of the catalyst and amine production

4 1. General Procedures All experiments were carried out under argon atmosphere. The syntheses and the treatments of the surface species carried out using high vacuum lines (< 10-5 mbar) and glove-box techniques under argon athmospher. Elemental analyses were performed at the Mikroanalytisches Labor Pascher and KAUST Analytical Corelab. Zr(NMe 2 ) 4 was purchased from Sigma Aldrich. Pentane was collected from a Solvant Purification System following by a freez-pump. Solid State Nuclear Magnetic Resonance Spectroscopy: One dimensional 1 H MAS and 13 C CP-MAS solid state NMR spectra were recorded on a Bruker AVANCE III spectrometer operating at 400 MHz for 1 H, with a conventional double resonance 4mm CPMAS probe. The samples were introduced under argon into zirconia rotors, which were then tightly closed. The spinning frequency was set to 17 for 1 H and 10 KHz for 13 C spectra, respectively. NMR chemical shifts are reported with respect to TMS as an external reference for 1 H, 13 C. For CP/MAS 13 C NMR, the following sequence was used: 90 0 pulse on the proton (pulse length 2.4 s), then a cross-polarization step with a contact time typically 2 ms, and finally acquisition of the 13 C signal under high power proton decoupling. The delay between the scan was set to 5 s, to allow the complete relaxation of the 1 H nuclei and the number of scans was between 3,000-5,000 for carbon, 100,000 for 15 N and 32 for proton. An apodization function (exponential) corresponding to a line broadening of 80 Hz was applied prior to Fourier transformation. 1 H- 1 H multiple-quantum Spectroscopy: Two-dimensional double-quantum (DQ) experiment was recorded on Bruker AVANCE III spectrometer with a conventional double resonance 3.2 mm CPMAS probe, according to the following general scheme: excitation of DQ coherences, t1 evolution, Z-filter, and detection. The spectra were recorded in a rotor synchronized fashion in t1; that is the t1 increment was set equal to one rotor period (4.545 μs). One cycle of the standard back-to-back (BABA) recoupling sequence was used for the excitation and reconversion period. Quadrature detection in w1 was achieved using the States-TPPI method. A spinning frequency of 22 KHz was used. The 90 0 proton pulse length was 2.5 μs, while a recycle delay of 5 s was used. A total 128 t1 increments with 32 scan each were recorded. Details about figure 2: (A) 1D 1 H spin-echo MAS solid state NMR spec-trum of 2 (acquired on a 600 MHz NMR spectrometer under a 20 KHz MAS spinning frequency, number of scans = 8, repetion delay = 5 s) (B) 2D 1H-1H double-quantum (DQ)/single-quantum (SQ) and (C) 1H-1H triple-quantum (TQ)/SQ (acquired on a 600 MHz NMR spectrometer under 22 KHz MAS spinning frequency with a back-to-back re-coupling sequence, number of scans = 128, repetition delay = 5 s number of t1 increments = 128, with the increment set equal to one rotor period of μs). Details about figure 3 and 4: (A) 13 C CP/MAS NMR spectrum of 2 (acquired on 600 MHz NMR spectrometer with 10 KHz MAS, number of scan = 20000, repetition delay = 4 s contact time = 2 ms, line broadening = 80 Hz). (B) 2D 3

5 CP/MAS HETCOR NMR spectrum with short contact times of 0.2 ms under 8.5 KHz MAS, number of scans per incriment = 4000, repetition delay = 4 s, number of t1 increments = 32, line broadening = 80 Hz). Details about figure 5: 2D 13 C- 13 C spin-diffusion with DARR (dipolar-assisted rotational resonance) of 2 obtaining with a mixing time τmix = 40ms. Sequence begins with CP using a ramped pulse on the 13C channel (acquired with 900 MHz NMR spectrometer with an 20 KHz MAS frequency, 2000 scans per t1 increment, a 3 s repetition delay, 128 individual increments and 4 ms contact time). Fourier Transformed Infrared Spectroscopy. FTIR spectra were recorded on a Nicolet 6700 FT-IR spectrometer equipped with a cell under controlled atmosphere. Typically, 16 scans were accumulated for each spectrum (resolution 4 cm -1 ). Preparation of Si-O-Zr(NMe 2 )(HNMe 2 )(NMeCH 2 ) (1): In a double shclenk, mg of Zr(NMe 2 ) 4 in slight excess (1.1 eq.) with respect to the amount of surface accessible silanols (0.3 mmol silanols groups per gram) was reacted with 3 g of SiO at room temperature in pentane for 1 h. After filtration and four washing cycles, all volatile compounds were evaporated and the white solid was dried for 1 h under dynamic vacuum (< 10-5 mbar). Preparation of Si-O-Zr(HNMe 2 )(ɳ 2 NMeCH 2 CH(Me)CH 2 )(NMe 2 ) (2): In a glass reactor (230 ml), an excess of drayed propylene gas (0.8 mbar) was reacted with 1 g of (1). The reaction was heated with the gradient room temperature to 150 C (1 C per minute) and then at 150 C for 24 hours. After reaction the remaining gas was analyzed by GCGCMS and contained only propylene. It was then evacuated for 1 h under dynamic vacuum (< 10-5 mbar). Alkylation of dimethyl amine with propene In a glove box, a glass reactor tube (230 ml) was charged with 1 (840 mg, 0.22 mmol, 0.08 eq.). The reactor was evacuated using a high vacuum line. 0.3 bar of propene (2.81 mmol, 1 eq.) was introduced first and condensed by cooling with liquid nitrogen. 0.4 mbar of HNMe 2 +H 2 were then added. After closing the reactor, the mixture was heated (150 C). The reaction mixture was heated for 20 h and then was cooled to 22 C. After reaction, the gas phase was analyzed by GC-FID and GC-MS. 2. Elemental analysis Table S1. Elemental analysis of 2. C/N N/Zr C/Zr %C %H %N %Zr

6 3. Solid State Nuclear Magnetic Resonance Spectra Figure S1. 1 H SS NMR and 13 C SS NMR spectra of 1 and 2 Figure S2A. 1H SS NMR spectra of 2 on SBA700 surface 5

7 Figure S2B : 1H MAS NMR, 2D contour plots of the aliphatic region of the DQ and TQ quantum proton SS-NMR correlation spectra of 2 on SBA 700 surface 4. Regeneration of the catalyst and amine production Time (min) (d) (c) (b) (a) 6

8 Figure S3. GC-FID Chromatogram of (a) HNMe 2 and (b) gas mixture after 1st reaction of HNMe 2 and 2 (c) 2nd reaction (d) 3rd reaction (C) (b) (a) Figure S4. GC-FID Chromatogram of (a) gas mixture after reaction of HNMe 2 and 2 (b) N,2-dimethylpropan-1-amine (d) HNMe 2 Figure S5. GC/Ms Characterization of the gas-phase products obtained after reaction of 2 with HNMe 2+H 2 7

9 1: Figure S6. Mass spectrum of diethylamide 2: Figure S7. Mass spectrum of 1-propanamine,N,2-dimethyl 8

10 b) a) wavenumbers (cm-1) Figure S8. FTIR of a) SiO b) After treating the SiO -700 with HNMe 2 and 1-propanamine,N,2-dimethyl, dimethylamine and hydrogen at 150 C during 20h then eveacuating (10-4 mbar) over night at 150 C 9

11 Figure S9. 1 H NMR of N-methylisobutylamine on methanol-d4 10

12 Figure S C NMR of N-methylisobutylamine on methanol-d4 11