Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key
Intermediate in Catalytic Hydroaminoalkylation Reactions
Item Type Article
Authors Hamzaoui, Bilel;Pelletier, Jeremie;El Eter, Mohamad;Chen, Yin;Abou-Hamad, Edy;Basset, Jean-Marie
Citation Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic
Hydroaminoalkylation Reactions 2015:n/a Advanced Synthesis &
Catalysis Eprint version Post-print
DOI 10.1002/adsc.201500484
Publisher Wiley
Journal Advanced Synthesis & Catalysis
Rights This is the peer reviewed version of the following article:
Hamzaoui, B., Pelletier, J. D. A., El�Eter, M., Chen, Y., Abou-Hamad, E. and Basset, J.-M. (2015), Isolation and Characterization of Well-Defined Silica-Supported Azametallacyclopentane: A Key Intermediate in Catalytic Hydroaminoalkylation Reactions. Adv. Synth. Catal., which has been published in final form at http://doi.wiley.com/10.1002/
adsc.201500484. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self- archiving.
Download date 2024-01-27 17:18:39
Link to Item http://hdl.handle.net/10754/578864
Supporting Information
1 Supplementary Materials
Isolation and characterisation of well-defined silica-
supported 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: [email protected]
†King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering, KAUST Catalysis Center, Thuwal 23955-6900, Saudi Arabia.
2 Supporting Information: Table of Contents
Contents
1. General Procedures ... 3
2. Elemental analysis ... 4
3. Solid State Nuclear Magnetic Resonance Spectra ... 5
4. Regeneration of the catalyst and amine production ... 6
3
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(NMe2)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 1H MAS and 13C CP-MAS solid state NMR spectra were recorded on a Bruker AVANCE III spectrometer operating at 400 MHz for 1H, 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 1H and 10 KHz for 13C spectra, respectively. NMR chemical shifts are reported with respect to TMS as an external reference for 1H, 13C. For CP/MAS 13C NMR, the following sequence was used: 900 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
13C signal under high power proton decoupling. The delay between the scan was set to 5 s, to allow the complete relaxation of the 1H nuclei and the number of scans was between 3,000-5,000 for carbon, 100,000 for 15N and 32 for proton. An apodization function (exponential) corresponding to a line broadening of 80 Hz was applied prior to Fourier transformation.
1H-1H 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 900 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 1H 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 45.45 μs).
Details about figure 3 and 4: (A) 13C 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
4
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 13C-13C 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(NMe2)(HNMe2)(NMeCH2) (1):
In a double shclenk, 264.85 mg of Zr(NMe2)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 SiO2 700 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(HNMe2)(ɳ2NMeCH2CH(Me)CH2)(NMe2) (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 HNMe2+H2 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 12 3.26 0.27 2.77 3.28 9.12
%H 1 0.71 0.71 3 3 9
%N 14 1.37 0.09
%Zr 91 2.71 0.02
5
3. Solid State Nuclear Magnetic Resonance Spectra
Figure S1. 1H SS NMR and 13C SS NMR spectra of 1 and 2
Figure S2A. 1H SS NMR spectra of 2 on SBA700 surface
6
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 SBA700
surface
4. Regeneration of the catalyst and amine production
3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0
(a) (b)
(c) (d)
Time (min)
7
Figure S3. GC-FID Chromatogram of (a) HNMe2 and (b) gas mixture after 1st reaction of HNMe2 and 2 (c) 2nd reaction (d) 3rd reaction
Figure S4. GC-FID Chromatogram of (a) gas mixture after reaction of HNMe2 and 2 (b) N,2-dimethylpropan-1-amine (d) HNMe2
Figure S5.GC/Ms Characterization of the gas-phase products obtained after reaction of 2 with HNMe2+H2
1 2 3 4 5 6 7
(a) (b)
(C)
8
Figure S6.Mass spectrum of diethylamide
Figure S7.Mass spectrum of 1-propanamine,N,2-dimethyl
1:
2:
9
Figure S8.FTIR of a) SiO-700. b) After treating the SiO-700 with HNMe2 and 1-propanamine,N,2-dimethyl, dimethylamine and hydrogen at 150°C during 20h then eveacuating (10-4 mbar) over night at 150°C
3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 wavenumbers (cm-1)
3319 3332
2962 2908
2862 2814 2885 2987
2943
) a
) b
10
Figure S9. 1H NMR of N-methylisobutylamine on methanol-D4
11
Figure S10. 13C NMR of N-methylisobutylamine on methanol-D4
