The authors would like to express their thanks to the King Abdullah University of Science and Technology (KAUST) for financial and human support.

1. Leak check for all the high vacuum vessels and their connection to the HVL
<ol>
	<li>Connect the vessel to the HVL.</li>
	<li>Check whether the pressure increases by alternating the dynamic and the static vacuum.</li>
	<li>In case of a leak, scan the connection with the high-frequency generator to localize leaks and holes.</li>
</ol>
2. Dehydroxylated silica preparation
<ol>
	<li>Cover fumed silica (5 g in a 100 mL beaker) with enough deionized water (ca. 50 mL) till it becomes a compact gel.</li>
	<li>Cover the beaker with some aluminum foil and heat it in the oven at 200 &#176;C overnight.</li>
	<li>Grind the silica and transfer (1 g) to a glass reactor (30 cm in height, with a diameter of 4 cm); then, close it with a cap and seal it with grease.</li>
	<li>Connect the glass reactor to the port of the HVL.</li>
	<li>Start heating it gradually to reach 700 &#176;C and leave it overnight.</li>
	<li>Let the reactor cool down and transfer it to the glovebox.</li>
	<li>Prepare a disc pellet from the silica dehydroxylated at 700 &#176;C for a transmission FTIR measurement in the glovebox.</li>
	<li>Observe the isolated silanol signal in the FTIR spectrum.</li>
</ol>
3. Solvent preparation (removal of oxygen and moisture)
<ol>
	<li>Prepare sodium-mirror-coated solvent bomb equipped with a Teflon stopcok.</li>
	<li>Transfer pentane to the solvent bomb.</li>
	<li>Connect the solvent bomb to the HVL.</li>
	<li>Check for leaks in the connections.</li>
	<li>Freeze the solvent using a liquid-nitrogen-filled dewar.</li>
	<li>Evacuate till the solvent finishes to degas.</li>
	<li>Stop the evacuation.</li>
	<li>Repeat the freeze (step 3.5); then, perform a degas cycle (steps 3.6 and 3.7) at least 2x more to ensure all gases are removed.</li>
</ol>
4. General procedure for grafting metal complexes on dehydroxylated silica using Hf(NMe2)4
<ol>
	<li>Dry a double Schlenk by evacuating it with the HVL and heating it with a heat gun.</li>
	<li>Put the dry double Schlenk into the glovebox.</li>
	<li>In the double Schlenk, add the precursor complex Hf(NMe2)4 (0.33 mmol, 0.089 mL) to one compartment and the dehydroxylated silica (1 g) to the other side with a stir bar.</li>
	<li>Close the two necks of the double Schlenk with cap and seal them with grease.</li>
	<li>Using a T-joint, connect the HVL to the solvent Schlenk on one side and to the double Schlenk on the other side.</li>
	<li>Ensure that all connections are secured by metallic clips and evacuate the line and the double Schlenk until reaching a stable high vacuum (10-5 mbar). All stopcocks should be evacuated.</li>
	<li>Transfer the solvent from the solvent Schlenk to the compartment of the double Schlenk containing the metal precursor by distillation. Once the glassware assembly is under static vacuum, use a liquid nitrogen dewar to cool the compartment to condense the solvent and to dissolve the precursor there.</li>
	<li>Transfer the solution to the silica compartment by gravitation. Stir it for 1&#8211;3 h to complete grafting.</li>
	<li>Introduce extra solvent by distillation to wash the silica.</li>
	<li>Start by washing the material; then, filter the material by transferring the solvent to the solvent compartment and distill the solvent to the solid compartment.</li>
	<li>Remove the waste solvent by distillation using an interceptor (solvent trap). Dry the material by using an HVL with continuous stirring in the beginning; then, leave it under a vacuum overnight.</li>
	<li>Prepare a disc pellet (50-70 mg of prepared material) for an FTIR measurement in the glovebox.</li>
</ol>
5. Preparation of the catalyst
<ol>
	<li>Add the grafted material (1 g) to a Schlenk. Connect it to the HVL.</li>
	<li>Start heating it gradually to reach 200 &#176;C and leave it for 4 h. Leave it to cool down under vacuum.</li>
	<li>Prepare a disc pellet (50-70 mg of prepared material) for an FTIR measurement in the glovebox.</li>
</ol>
6. Imine metathesis catalysis
<ol>
	<li>In an ampule tube (or sealed vial), add the catalyst (0.0031 mmol, 12.47 mg).</li>
	<li>Add two imine substrates, for example, N-(4-phenylbenzylidene)benzylamine (0.0783 mmol, 21.36 mg) with N-benzylidene-tert-butylamine (0.0783 mmol, 13.94 uL). Or, use N-(4-fluorobenzylidene)-4-fluoroaniline (0.0783 mmol, 17.00 mg) with N-(4-phenylbenzylidene)benzylamine (0.0783 mmol, 21.36 mg).</li>
	<li>Add 0.5 mL of toluene. Add a stirring bar. Connect the ampule tube to the vacuum line. Freeze the ampule tube by using liquid nitrogen.</li>
	<li>Use the flame torch (oxygen and propane) to seal the ampule tube. For a sealed vial, just close it tightly by the compressor.</li>
	<li>Place the tube in oil or in a sand bath at 80 &#176;C.</li>
	<li>Leave the experiment run for up to 6 h. Monitor the reaction at different time from 1 to 6 h.</li>
	<li>Freeze the tube and cut the top using a glass cutter.</li>
	<li>Filter the solution into a gas chromatography (GC) vial for GC mass spectrometry (GC-MS) analysis. Dilute the reaction solution to a volume of 1 mL.</li>
</ol>

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The authors have nothing to disclose.

The methodology employed in SOMC was developed to handle sensitive materials (such as highly dehydroxylated silica and sensitive complexes precursors, etc.) in the cleanest way possible. This is necessary to prepare and characterize single-site well-defined surface complexes. Furthermore, these complexes can be isolated and serve as intermediates to various catalytic transformations of interest (e.g., alkane metathesis4,5, imine metathesis7,8,32, and hydroaminoalkylation26).
HVLs (producing a vacuum as high as 10-5 mbar) are necessary to avoid any contamination from inert gases during the grafting reactions. High vacuum techniques are very different from the positive pressure techniques employed in regular Schlenk lines or even gloveboxes. Due to its high surface area (200 m2 per gram), silica tends to adsorb contaminants (water, etc.) that can compromise subsequent reactions.
The glovebox is used mostly to load/unload reactants prior to the reactions and to conduct some reactions. All gloveboxes in this method operate under argon as some catalysts can react with nitrogen. The method requires special attention dedicated to transferring sensitive materials from gloveboxes to HVLs and back. Some steps (i.e., liquid addition and solid washing) require the user to assemble several pieces of glassware on the HVL. Each connection must remain leak-free for the time of the operation (i.e., during the solvent transfer) to protect the chemicals contained.
This technique is rather time-consuming and challenging to upscale but remains unparalleled in producing a significant amount (1-3 g) of clean and well-characterized surface complexes that can be used as catalysts. Future development foreseen is the use of this method to isolate more new catalytic species, such as those containing SOMFs (i.e., metal-nitrido fragment M&#8801;N).
In this study, a SOMF metal amide fragment was isolated. Highly dehydroxylated silica SiO2-700 was treated with about one equivalent of metal precursor (Hf(NMe2)4 [0.089 mL]) to the amount of silanol (0.3 mmol&#183;g-1) in pentane at room temperature to afford catalysts7,8,32. The volatiles were removed, and the powder samples were dried under a dynamic vacuum to afford the desired materials, which were heated to 200 &#176;C to generate imido. All materials should be characterized by FTIR, elemental microanalysis, and SSNMR and DNP-SENS.
The surface silanols were almost completely consumed as evidenced by the disappearing of the signal at 3,747 cm-1 in the FTIR spectra of the grafted complexes. New signals observed around 2,800-3,000 cm-1 and 1,400-1,500 cm-1 correspond to alkyl groups. Further studies by CHNS and ICP analysis provide information about the metal loading for complex 1 (4.49% of Hf in weight per gram of silica (0.91 mmol of Hf per silanol)) that is consistent with a monopodial species. The expected and found M/C, M/H, and M/N ratios are N/M = 3.9 (theory = 3) and C/M = 7.1 (theory = 6) for the grafted material 1 (see Table 1); for 2, the N/M and C/M ratios are 2.5 (theory = 2) and 4.6 (theory = 4), respectively.
To get an insight into the coordination sphere of the surface grafted metal complexes, the materials were examined by advanced SSNMR spectroscopy experiments and DNP-SENS studies. SSNMR results are generally more difficult to interpret compared to liquid NMR spectroscopy; SSNMR is for insoluble macromolecules. Solid samples have less isotropic molecular tumbling compared to liquid samples; the molecules can tumble in all directions as they are homogeneous and diamagnetic, which will result in much broader signals in SSNMR for solid samples40.
From DQ SSNMR, we could observe -CH2 and -CH3,&#160;but from TQ SSNMR, only -CH3 was presented, and from HETCOR correlation, we could elucidate the structure. We focused on the metal-nitrogen fragment which was delivered by the use of 15N DNP-SENS, since we were working on amine complexes.
To conclude, the preparation of new silica-supported hafnium complexes [(&#8801;Si-O-)Hf(&#951;2-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)] 1, and [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] 2 fully characterized by SS NMR and FTIR spectroscopies and elemental analysis. Further characterizations were carried giving structural information about nitrogen atom by 15N MAS DNP SENS data. The data show the presence of surface fragments (MNC) in 1, and ([M]=N) fragment in 2. The essential role of ([M]=NR) fragment in imine metathesis was demonstrated in catalyst testing with two pairs of imine substrates.

SOMC has a rich library of surface complexes active for a wide range of catalytic reactions and an unparalleled track record to isolate the catalytic intermediates in heterogeneous catalysis. Single-site catalysts have been prepared by the reaction of an organometallic compound (or a coordination compound) with a very clean surface of highly dehydroxylated metal oxide (e.g., silica). Recently, we have identified surface organometallic fragments (SOMF) (e.g., M=C, M-C, M-H, M-NC, M=O, M=CR2,andM=NR) that have a pivotal role toward targeted catalysis reactivity (e.g., alkane oxidation1,2,3, alkane metathesis4,5, alkene metathesis6, imine metathesis7,8,9). [M]=NR fragments have received less attention; their characterization and reactivity studies remain limited, yet they can act as an intermediate in carbon-nitrogen transformation reactions10. The importance of imido complexes (bearing a [M]=NR) is their well-established organic synthesis and catalysis11,12. Stoichiometric or catalytic reactions may occur at the M=NR fragment itself13, or the imido group may remain a spectator, as in Schrock&#39;s catalysts for olefin metathesis14 or some Ziegler-Natta-type olefin polymerization catalysts15. This paper deals with a reaction of imine metathesis with a group IV organometallic complex bearing a metallaaziridine fragment which transfers to a metal-imido fragment that promotes the catalysis16. Catalytic imine metathesis is analogous to olefin metathesis in that two different imines afford a statistical mixture of all possible =NR exchange products.
Metathesis reactions were discovered in 196417 by Phillips Petroleum Co., Bartlesville, Oklahoma. A variety of heterogeneous catalysts were developed for olefin metathesis (e.g., tungsten, molybdenum oxide on silica or alumina, or rhenium oxide on alumina)18. Most progresses were reported in olefin metathesis19,20 and advanced the general understanding of hydrocarbon transformations. They were recognized in 2005 by the award of the Nobel Prize to scientists who worked in olefin metathesis, namely Richard R. Schrock, Yves Chauvin, and Robert Grubbs21. The chemistry of metal-alkylidene-mediated olefin metathesis processes has broadened not only pure hydrocarbon organic synthesis possibilities22 but also made it possible to deliver chemicals with new carbon-heteroatom double bonds7,16. Alkane metathesis was discovered later by Basset&#39;s group and requires multifunctional catalysts23,24,25. Less attention has been dedicated to imine metathesis, yet it can be a promising route to a variety of nitrogen-containing compounds.
Metal-mediated catalytic systems can selectively metathesize carbon-nitrogen bonds26,27,28. Homogeneous catalytic systems have been employed for imine metathesis, yet no definite mechanism has been validated29. This has hindered the rational development of new efficient synthetic pathways to yield new compounds. A practical perspective developing a metal-catalyzed imine metathesis may improve its selectivity and its tolerances toward functional groups compared to acid-catalyzed imine exchange30,31.
Employing rigorous SOMC methodology, we have isolated two new well-defined hafnium nitrogen-containing fragments (metallaaziridine and metal-imido) that were fully characterized (FTIR, solid-state NMR, elemental microanalysis)7. Using highly dehydroxylated silica with isolated silanols, SiO2-700 (Figure 1) allows the isolation of well-defined single-site catalysts. This work is considering the M-N, MNC, and M=N surface fragments (SFs) as key reaction intermediates that direct the reaction toward hydroaminoalkylation26 or imine metathesis7,8,32. This study can potentially bring a better general understanding of transition metal imido functional groups bore by group IV metal grafted on silica.
One major issue with a heteroatom containing SFs, including nitrogen ones, has been the limited amount of characterization methods available to identify the metal-heteroatom coordination. This work is showing that 15N DNP-SENS can provide a clear insight into the silica-supported nitrogen moieties (metallaaziridine and metal-imido). Herein, we isolate a silica-supported well-defined (imido) complex and demonstrate its capability as a highly efficient imine metathesis catalyst7,33.
Overall, this work leads to an improved understanding of the imine metathesis mechanism catalyzed by surface complexes. This protocol can be generalized to other early transition metal imine complexes grafted on highly dehydroxylated silica surfaces. Those surface species could be employed as catalysts but only for the hydroamination and hydroaminoalkylation of alkenes or alkynes26,34,35,36,37, but also for the metathesis of imines representing a 2 + 2 mechanism including the imine and the imido groups see (Figure 2). Imine products are valuable in pharmaceutical and agricultural applications35,38.

<table><tbody><tr><td>Fumed silica (AEROSIL&amp;reg; 200)</td><td>Sigma-Aldrich</td><td>112945-52-5</td><td></td></tr><tr><td>tetrakis(dimethylamido)hafnium(iv) Hf(NMe&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;</td><td>Strem Chemicals</td><td>19782-68-4</td><td></td></tr><tr><td>Pentane</td><td></td><td>109-66-0</td><td></td></tr><tr><td>Nicolet 6700 FT-IR spectrometer</td><td>Thermo Scientific</td><td>IQLAADGAAGFAEFMAAI</td><td>equipped with a controlled-atmosphere cell</td></tr><tr><td>Ultashield 600WB plus 600 MHz NMR Bruker AVANCE III solid-state NMR spectrometer</td><td>Bruker</td><td>-</td><td>Magnet BZH 09/600/107B</td></tr><tr><td>5110 ICP-OES</td><td>Agilent Technologies</td><td>G8015A</td><td>EPA 3052 method for digestion</td></tr><tr><td>Ethos1 (Advanced Digestion System)</td><td>Milestone</td><td>-</td><td></td></tr><tr><td>Gass Chromatography (GC)</td><td>Agilent Technologies</td><td>G1701EA</td><td>inert XL MSD With Triple-Axis Detector</td></tr><tr><td>DNP-SENS-NMR 400 MHz (1H/electron Larmor frequencies) Bruker Avance III solid-state NMR spectrometer</td><td>Bruker</td><td>-</td><td>equipped with a 263-GHz gyrotron.</td></tr><tr><td>FLASH 2000 CHNS/O Analyzer</td><td>Thermo Scientific</td><td>-</td><td></td></tr><tr><td>N-(4-Phenylbenzylidene)benzylamine</td><td>Sigma-Aldrich</td><td>118578-71-5</td><td></td></tr><tr><td>N-(4-Fluorobenzylidene)-4-fluoroaniline</td><td>Sigma-Aldrich</td><td>39769-09-0</td><td></td></tr><tr><td>N-Benzylidenetert-butylamine</td><td>Sigma-Aldrich</td><td>6852-58-0</td><td></td></tr><tr><td>Toluene</td><td>Sigma-Aldrich</td><td>108-88-3</td><td></td></tr></tbody></table>

imine metathesis by silica-supported catalysts using the methodology of surface organometallic chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

Firstly, preparing silica 700 as described in section 2 of the protocol, the fumed silica should be mixed with enough deionized water to make it compact, left overnight in the oven at 120 &#176;C, and then, loaded to a quartz reactor (Figure 3). Dehydroxylated silica SiO2-700 was obtained by heating the silica gradually to 700 &#176;C under a dynamic vacuum, FTIR spectrum for SiO2-700 in (Figure 1) shows the characteristic isolated silanol of SiO2-700.
The grafting of metal complex to the silica was achieved by a protonolysis reaction of the amido ligands (NMe2) by surface silanols. For the grafting of organometallic complexes onto highly dehydroxylated silica surface SiO2-700 (Figure 4), dehydroxylated silica was loaded with complex Hf(NMe2)4 into a double Schlenk inside a glovebox. The double Schlenk was moved out of the glovebox for the reaction to occur. The grafting reaction lasted around 3 h. Three washing cycles were then carried out by filtration; more solvent was transferred by distillation when needed. Finally, the solvent was distilled and then removed, with all volatiles, using an interceptor (solvent trap). All solids were dried by connecting the double Schlenk to the HVL (Figure 4 and Figure 5).
Elemental analysis using inductively coupled plasma (ICP) (using the EPA 3052 method for digestion) and carbon, hydrogen, nitrogen, and sulfur analyzer (CHNS) accompanied with FTIR was first verified for the determination of grafting stoichiometry. Elemental analysis showed that N/M = 3.9 (theory = 3) and C/M = 7.1 (theory = 6) for the grafted material (see Table 1); for 2, the N/M and C/M ratios were 2.5 (theory = 2) and 4.6 (theory = 4), respectively. Thus, the carbon and nitrogen contents were declined. For the preparation of the samples for the FTIR measurement, using the designed FTIR cell, see Figure 6. The first sample is the dehydroxylated SiO2-700, which displayed a characteristic peak for isolated silanol. After grafting the complex on dehydroxylated silica, this characteristic peak almost completely disappeared, and new peaks appeared in the alkyl region at 2,776-2,970 cm-1 and 1,422-1,465 cm1. After a heat treatment of prepared material at 200 &#176;C for 1 h, its infrared (IR) spectrum showed a new peak for the imido fragment at 1,595 cm-1.
SSNMR experiments were carried out for a deeper understanding of the surface structure. Samples for SSNMR (Figure 7) were loaded in a specific rotor (32.1 &#181;L). The 1H SSNMR spectrum of the grafted material displayed broad peaks at 2.2 and 2.7 ppm for alkyl groups bonded to the nitrogen ligands. The breadth of the resonances was expected in 1H SSNMR (in contrast to liquid NMR) and was also associated with less mobile surface species (Figure 7B).
The 13C cross-polarized magic angle spinning (CP-MAS) spectrum displayed signals that were less broadened but had a low sensitivity (alike liquid NMR). The spectrum of the grafted material revealed two overlapping peaks at 37 ppm -N-(CH3)2 and at 46 ppm, attributed to the nonequivalent methyl group in -N-(CH3) alongside a low-intensity peak at 81 ppm. A heteronuclear correlation spectroscopy (HETCOR) experiment was carried out to show the correlation between proton and carbon directly bonded to each other. The 81 ppm signal was correlated with the proton peak at 2.7 ppm in the HETCOR spectrum7. As previously reported with zirconiaaziridene, this peak represented the methylene (CH2) group in a metallaaziridine cycle39.
A multiple-quantum experiment makes it possible to visualize the correlation between proximal protons. Double-quantum (DQ) NMR indicates the sum of the two single quantum NMR frequencies to provide an autocorrelation peak located where &#969;1 = 2&#969;2. Similarly, for triple-quantum (TQ) NMR impart from the sum of three protons single quantum frequencies where &#969;1 = 3&#969;2. CH2 and CH3 afford characteristic autocorrelation peaks in the double- and triple-quantum dimensions, respectively. DQ and TQ proton SSNMR experiments were performed with the grafted material. For the strongest autocorrelation peak observed for the signal at 2.2 ppm in both the DQ and TQ spectra (appearing at 4.4 ppm and 6.6 ppm in DQ and TQ, respectively), revealing -CH3 protons, see Figure 7B. The second overlapping peak for the proton at 2.7 ppm showed an autocorrelation only in the double quantum (DQ) spectrum; thus, it confirms the presence of a methylene group (-CH2-) in the grafted species.
15N SSNMR experiments using the DNP-SENS technique (Figure 7B) were carried out to characterize the nitrogen atoms coordinated to the metal center. The spectrum obtained for the grafted material displayed two peaks, around 7 and 32 ppm. On the basis of its relative intensity, the intense signal downfield at 32 ppm was assigned to the nitrogen nuclei of the (&#951;2-NMeCH2) and (-NMe2) functionalities. The weak upfield-shifted peak at 7 ppm was attributed to an NH(CH3)2 moiety; upon heat treatment, -HNMe2 remains on the surface.
For the imido metal fragment in catalyst 2, generated after heat treatment, one broad peak appeared at 2.2 ppm, and the weak peaks at 1.2 and 0.7 ppm in the 1H NMR spectrum attributed to some minor impurities, dimethylamine moieties. For 13C CP-MAS, NMR spectrum displays two peaks at 37 and 48 ppm. Interestingly, the peak for (-CH2-) in metallaaziridine disappeared (Figure 7C). Additionally, we inferred from the multiple quantum experiments that the 1H peak appearing at 2.2 ppm represented the (-CH3) protons. For the 15N SSNMR spectrum of the imido metal fragment in 2 (Figure 7C), an additional downfield-shifted peak at 113 ppm along with a peak at 34 ppm became much less intense after the heat treatment of the grafted material. The 113 ppm peak was assigned to the new fragment generated from the hafnium imido moieties.
In a glovebox, imine substrates with a catalyst were loaded either in an ampule tube or a sealed vial with toluene, and Figure 8 shows the reaction of imine metathesis with three imine compounds, namely N-(4-phenylbenzylidene)benzylamine, N-(4-fluorobenzylidene)-4-fluoroaniline, and N-benzylidenetert-butylamine. Mass spectra for products analyzed by GC-MS (Figure 8) are a&#34; (1-([1,1&#39;-biphenyl]-4-yl)-N-(tert-butyl)methanimine), c&#39; (N,1-diphenylmethanimine),&#160;a&#39; (1-([1,1&#39;-biphenyl]-4-yl)-N-(3-fluorophenyl)methanimine) and b&#39; (1-(4-fluorophenyl)-N-phenylmethanimine).
Imine metathesis is a combination of two imine substrates mixed with the catalyst to produce a new two imine substrates after characterizing by GC-MS. To calculate the conversion percentage as shown in (Table 2), use the following formulas. 
<img alt="Equation 1" src="/files/ftp_upload/59409/59409eq1.jpg" /> 
<img alt="Equation 2" src="/files/ftp_upload/59409/59409eq2.jpg" />
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/59409/59409fig1.jpg" /> 
Figure 1: Dehydroxylation. Formation of isolated silanols by dehydroxylation to produce silica dehydroxylated at 700 &#176;C (SiO2-700). <a href="https://www.jove.com/files/ftp_upload/59409/59409fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/59409/59409fig2.jpg" /> 
Figure 2: General reaction scheme of the imine metathesis mechanism7. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/59409/59409fig3.jpg" /> 
Figure 3: Dehydroxylation of silica. The reactor was inserted into the oven and connected to a high vacuum line (HVL). The photograph shows the actual setup. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/59409/59409fig4.jpg" /> 
Figure 4: Grafting in a double Schlenk. Schematic representation of the grafting process. The photograph shows the actual setup. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/59409/59409fig5.jpg" /> 
Figure 5: Handling grafting in a double Schlenk with a high vacuum line (HVL). First, the solvent transfer procedure was performed, followed by the washing procedure, the solvent removal, and drying the material. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig5large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/59409/59409fig6.jpg" /> 
Figure 6: Fourier-transform infrared spectroscopy (FTIR) measurement. (A) FTIR disc pellet preparation. (B) FTIR spectra of the support, SiO2-700 have a characteristic signal for isolated silanols observed at 3,747 cm-1 and silica undertone between 1,400-2000 cm-1. For the grafted complex, strong new signals appeared in the regions of 2,800-3,000 cm-1 and 1,400-1,500 cm-1. They represent the alkyl groups. After heat treatment, spectrum shows a new signal appeared at 1,595 cm-1 for the imido group7. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig6large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/59409/59409fig7.jpg" /> 
Figure 7: NMR data from the grafted material and the catalyst. (A) Preparing a solid-state NMR sample. (B) (B-1) 1D 13C cross-polarized magic angle spinning (CP-MAS) with 2D 1H-13C heteronuclear correlation (HETCOR( NMR spectra of the grafted complex before treatment. (B-2) 1D 1H NMR spectrum with 1H-1H double-quantum (DQ) and 1H-1H triple quantum (TQ) spectra of the grafted complex. (B-3) 15N dynamic nuclear polarization surface enhanced the NMR spectroscopy (DNP-SENS) spectrum and (inset 1) the proposed structure of the grafted surface hafnium complex [(&#8801;Si-O-)Hf(&#951;2-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. (C) (C-1) 1D 13C CP-MAS with 2D 1H-13C HETCOR NMR spectra of the grafted complex after heat treatment to generate an imido fragment. (C-2) 1D 1H NMR spectrum with 1H-1H DQ and 1H-1H TQ spectra of the grafted complex after heat treatment which is the catalyst 2. (C-3) 15N DNP-SENS spectrum, and (inset 2) proposed a structure of the surface hafnium complex catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]7. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig7large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/59409/59409fig8.jpg" /> 
Figure 8: Imine metathesis catalysis and mass spectral data of products. Three imine compounds were tested: N-(4-phenylbenzylidene)benzylamine (a), N-(4-fluorobenzylidene)-4-fluoroaniline (b), and N-benzylidene-tert-butylamine (c). Gas chromatography-mass spectrometry (GC-MS) was used to analyze the products obtained, namely 1-([1,1&#39;-biphenyl]-4-yl)-N-(tert-butyl)methanimine (a&#34;), N,1-diphenylmethanimine (c&#39;), 1-([1,1&#39;-biphenyl]-4-yl)-N-(3-fluorophenyl)methanimine (a&#39;), and 1-(4-fluorophenyl)-N-phenylmethanimine (b&#39;)7. <a href="https://www.jove.com/files/ftp_upload/59409/59409fig8large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td></td>
			<td>Metal </td>
			<td>%Metal</td>
			<td>M/Silanol</td>
			<td>%C</td>
			<td>%N</td>
			<td>C/N</td>
			<td>N/M</td>
			<td>C/M</td>
		</tr>
		<tr>
			<td>1</td>
			<td>Hf</td>
			<td>4.94</td>
			<td>0.92</td>
			<td>2.49</td>
			<td>1.5</td>
			<td>2</td>
			<td>3.9</td>
			<td>7.1</td>
		</tr>
		<tr>
			<td>2</td>
			<td>Hf</td>
			<td>4.48</td>
			<td>0.81</td>
			<td>1.4</td>
			<td>0.8</td>
			<td>1.8</td>
			<td>2.5</td>
			<td>4.6</td>
		</tr>
	</tbody>
</table>
Table 1: Elemental analysis7.
<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Catalyst</td>
			<td>Time</td>
			<td>substrate conversion %</td>
			<td>Substrate conversion %</td>
		</tr>
		<tr>
			<td>2</td>
			<td>1</td>
			<td>a (54)</td>
			<td>c (54)</td>
		</tr>
		<tr>
			<td>no catalyst</td>
			<td>1</td>
			<td>a (11)</td>
			<td>c (11)</td>
		</tr>
		<tr>
			<td>2</td>
			<td>6</td>
			<td>a (50)</td>
			<td>b (55)</td>
		</tr>
		<tr>
			<td>no catalyst</td>
			<td>6</td>
			<td>a (25)</td>
			<td>b (20)</td>
		</tr>
		<tr>
			<td>2</td>
			<td>4</td>
			<td>a (36)</td>
			<td>b (30)</td>
		</tr>
	</tbody>
</table>
Table 2: Catalysis Conversion7.

Watch this Scientific Journal Video about Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry at JoVE.com

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

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9.5K Views.  King Abdullah University of Science and Technology (KAUST). Mijn protocol is belangrijk omdat het je in staat stelt om zeer nauwkeurige katalysator te maken, zeer selectief, die slechts één katalytische reactie kan doen. Het protocol is afgeleid van een concept van goed gedefinieerde, single-site katalysator, en deze single-site katalysatoren doen fantastische reacties. Deze techniek is uitdagend en tijdrovend, maar blijft ongeëvenaard in het voorbereiden van oppervlakte- of oppervlaktecomplexen die als katalysator kunnen worden gebruikt.En ...

Video: Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of novel materials. Coupled with analysis by in situ secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS), soft landing provides unprecedented insights into the interactions of well-defined species with surfaces.

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using ...

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Here, we present a protocol with a sol-gel process to synthesize gold intercalated in the walls of mesoporous materials (GMS), which is confirmed to possess a mesoporous matrix with gold intercalated in the walls imparting great stability and recyclability.

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties ...

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The silica-encapsulated metal oxide nanoparticles are then carburized in a methane/hydrogen atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal carbide nanoparticles. During the carburization process, the silica shells prevent the sintering of adjacent carbide nanoparticles while also preventing the deposition of excess surface carbon. Alternatively, the silica-encapsulated metal oxide nanoparticles can be nitridized in an ammonia atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal nitride nanoparticles. By adjusting the reverse microemulsion parameters, the thickness of the silica shells, and the carburization/nitridation conditions, the transition metal carbide or nitride nanoparticles can be tuned to various sizes, compositions, and crystal phases. After carburization or nitridation, the silica shells are then removed using either a room-temperature aqueous ammonium bifluoride solution or a 0.1 to 0.5 M NaOH solution at 40-60 &#176;C. While the silica shells are dissolving, a high surface area support, such as carbon black, can be added to these solutions to obtain supported early transition metal carbide or nitride nanoparticles. If no high surface area support is added, then the nanoparticles can be stored as a nanodispersion or centrifuged to obtain a nanopowder.

A &#8220;removable ceramic coating method&#8221; is presented in visual format for the synthesis of non-sintered and metal-terminated monometallic and bimetallic early transition metal carbide and nitride nanoparticles with tunable sizes and crystal structures.

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The ...

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at&#160;&#34;outer space conditions&#34; via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 &#176;C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl). The subhalide (e.g., SnCl) is trapped within a matrix of an inert solvent, like toluene at -196 &#176;C. Heating the solid matrix to -78 &#176;C gives a metastable solution of the subhalide. The metastable subhalide solution is highly reactive but can be stored at -78 &#176;C for several weeks. On heating the solution to room temperature, a disproportionation reaction occurs, leading to elemental tin and the corresponding dihalide. By applying bulky ligands like Si(SiMe3)3, the intermediate metalloid cluster compounds can be trapped before complete disproportionation to elemental tin. Hence, the reaction of a metastable Sn(I)Cl solution with Li-Si(SiMe3)3 gives [Sn10(Si(SiMe3)3)4]2- 1 as black crystals in high yield. 1 is formed via a complex reaction sequence including salt metathesis, disproportionation, and degradation of larger clusters. Further, 1 can be analyzed by various methods like NMR or single crystal X-ray structure analysis.

The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a ...

Preparation of Functional Silica Using a Bioinspired Method

The goal of the protocols described herein is to synthesize bioinspired silica materials, perform enzyme encapsulation therein, and partially or totally purify the same by acid elution. By combining sodium silicate with a polyfunctional bioinspired additive, silica is rapidly formed at ambient conditions upon neutralization. 
The effect of neutralization rate and biomolecule addition point on silica yield are investigated, and biomolecule immobilization efficiency is reported for varying addition point. In contrast to other porous silica synthesis methods, it is shown that the mild conditions required for bioinspired silica synthesis are fully compatible with the encapsulation of delicate biomolecules. Additionally, mild conditions are used across all synthesis and modification steps, making bioinspired silica a promising target for the scale-up and commercialization as both a bare material and active support medium.
The synthesis is shown to be highly sensitive to conditions, i.e., the neutralization rate and final synthesis pH, however tight control over these parameters is demonstrated through the use of auto titration methods, leading to high reproducibility in reaction progression pathway and yield. 
Therefore, bioinspired silica is an excellent active material support choice, showing versatility towards many current applications, not limited to those demonstrated here, and potency in future applications.

Here, we present a protocol to synthesize bioinspired silica materials and immobilize enzymes therein. Silica is synthesized by combining sodium silicate and an amine &#39;additive&#39;, which neutralize at a controlled rate. Material properties and function can be altered either by in situ enzyme immobilization or post-synthetic acid elution of encapsulated additives.

The goal of the protocols described herein is to synthesize bioinspired silica materials, perform enzyme encapsulation therein, and partially or totally ...

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst removal via host-guest interactions. The new NHC ligand possesses an adamantyl (guest) tethered linear ethylene glycol units for hydrophobic inclusion into the cavity of a &#946;-cyclodextrin (&#946;-CD) host compound. The new NHC ligand was applied to a Ru-based olefin metathesis catalyst. The Ru catalyst demonstrated excellent activity in representative ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions in aqueous media as well as organic solvent, CH2Cl2. After the reaction was complete, the lingering Ru residue was removed from the aqueous solution with the efficiency of more than 99% (53 ppm of Ru residue) by simple filtration utilizing a host-guest interaction between insoluble silica-grafted &#946;-CD (host) and the adamantyl moiety (guest) on the catalyst. The new Ru catalyst also demonstrated high removal efficiency via extraction when the reaction is run in organic solvent by partitioning the crude reaction mixture between layers of diethyl ether and water. In this way, the catalyst stays in aqueous layer only. In organic layer, the residual Ru amount was only 0.14 ppm in the RCM reactions of diallyl compounds.

A removable water-soluble N-heterocyclic carbene (NHC) ligand in aqueous media via host-guest interaction has been developed. We demonstrated representative olefin metathesis reactions in water as well as in dichloromethane. Via either host-guest interaction or extraction, the residual ruthenium (Ru) catalyst was as low as 0.14 ppm after the reaction.

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of the reaction site in metal-organic framework (MOF)&#8211;based catalysts in an enantioselective catalytic reaction system. Therefore, a method of validating the reaction site of MOF-based catalysts is necessary to investigate this issue. Substrate size discrimination by pore size was accomplished by comparing the substrate size versus the reaction rate in two different types of carbonyl-ene reactions with two kinds of MOFs. The MOF catalysts were used to compare the performance of the two reaction types (Zn-mediated stoichiometric and Ti-catalyzed carbonyl-ene reactions) in two different media. Using the proposed method, it was observed that the entire MOF crystal participated in the reaction, and the interior of the crystal pore played an important role in exerting chiral control when the reaction was stoichiometric. Homogeneity of the chiral environment of MOF catalysts was established by the size control method for a particle used in the Zn-mediated stoichiometric reaction system. The protocol proposed for the catalytic reaction revealed that the reaction mainly occurred on the catalyst surface regardless of the substrate size, which reveals the actual reaction sites in MOF-based heterogeneous catalysts. This method for reaction site validation of MOF catalysts suggests various considerations for developing heterogeneous enantioselective MOF catalysts.

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

Here, we present a protocol for active site validation of metal-organic framework catalysts by comparing stoichiometric and catalytic carbonyl-ene reactions to find out whether a reaction takes place on the inner or outer surface of metal-organic frameworks.

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...

Organocatalysis

Source: Vy M. Dong and Faben Cruz, Department of Chemistry, University of California, Irvine, CA
This experiment will demonstrate the concept of organocatalysis by illustrating the proper setup of a reaction that utilizes enamine catalysis. Organocatalysis is a form of catalysis that uses substoichiometric amounts of small organic molecules to accelerate reactions. This type of catalysis is complementary to other forms of catalysis such as transition metal or biocatalysis. Transition metal catalysis involves transition metals as catalysts and biocatalysis uses enzymes as catalysts. Some advantages of organocatalysis include the low toxicity and cost of the organocatalysts in comparison to many metal catalysts. In addition, most organocatalysts are not sensitive to air and moisture, unlike metal catalysts. In contrast to enzymes found in living organisms, the small molecules that act as organocatalysts are typically easy to access. Furthermore, organocatalysis offers complementary and new reactivity not observed with other forms of catalysis.

Organocatalysis: Principles and Applications

Source: Vy M. Dong and Faben Cruz, Department of Chemistry, University of California, Irvine, CA
This experiment will demonstrate the concept of ...

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Organic Chemistry II

Synthesis Of A Ti(III) Metallocene Using Schlenk Line Technique

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University&#160;
Inorganic chemists often work with highly air- and water-sensitive compounds. The two most common and practical methods for air-free synthesis utilize either Schlenk lines or gloveboxes. This experiment will demonstrate how to perform simple manipulations on a Schlenk line with a focus on solvent preparation and transfer. Through the synthesis of a reactive Ti(III) metallocene complex, we will demonstrate a new, simple method to degas solvent as well as how to transfer solvent by cannula and by syringe on a Schlenk line.
The synthesis of a Ti(III) metallocene compound 3 is shown in Figure 1.1 Compound 3 is highly reactive with O2, (see oxidation of compound 3 to Ti(IV) metallocene 4 shown in Figure 1). Therefore, it is important to run the synthesis under anaerobic conditions. The synthesis of target compound 3 can be monitored visually and progresses through one additional color change before arriving at the desired product, which is blue in color. If during the experiment there is an observed color change from blue to yellow (or green = blue + yellow), this is an indication that O2 entered the flask and that undesired oxidation of compound 3 to the Ti(IV) analog (compound 4) has occurred.
<img alt="Figure 1" src="/files/ftp_upload/10428/10428fig1v2.jpg" /> 
Figure 1. Synthesis of Ti(III) metallocene compound 3 and it&#39;s reaction with O2.

Synthesis Of A TiIII Metallocene Using Schlenk Line Technique

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University&#160;
Inorganic chemists often work with highly air- and water-sensitive ...

Inorganic Chemistry

Olefin Metathesis Polymerization: Overview

Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double&#160;bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a carbon-metal double bond, also known as carbene.
The olefin metathesis reaction follows the reversible mechanism as shown in the figure below:
<img alt="Figure1" src="/files/ftp_upload/12934/12934_PT_Figure_1.svg" style="text-align: center; height: 300px;" />
The general mechanism involves the reaction of Grubbs catalyst with an alkene in a [2+2] cycloaddition giving a four-membered metallacyclobutane intermediate which immediately undergoes a ring-opening reaction in a reverse manner to give back the starting material or by breaking different bonds to form a different carbene or a catalyst and a different alkene product.
The new catalyst undergoes [2+2] cycloaddition with a second alkene to form a new metallacyclobutane, giving the metathesis product and a new carbene complex. This new carbene complex is then ready to attack another molecule of starting material, and the cycle is repeated.
There are several ways the olefin metathesis has been implemented for polymer synthesis. However, ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) are the most widely used for polymerization. ROMP is a chain growth, addition polymerization reaction, whereas ADMET is a step-growth, condensation polymerization reaction.

Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

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