AP is grateful to Imperial College London for a PhD studentship via the Frankland Chair endowment. Johnson Matthey plc are also thanked for the loan of the precious metal salts used in this work.

Note: Carry out all syntheses in a fume hood, and only after appropriate safety issues have been identified and measures taken to protect against them. Personal protective equipment include a lab coat, gloves and safety goggles and should be worn at all times.
1. Synthesis of N,N,N-tris(diphenylphosphinomethylene)amine, N(CH2PPh2)3 (N-triphosPh) (1)
<ol>
	<li>To a 200 ml oven dried Schlenk flask add diphenyl(hydroxymethylene)phosphonium chloride11 (6.99 g, 24.7 mmol) and place under nitrogen via three sequential vacuum-nitrogen cycles on a dual-manifold Schlenk line.</li>
	<li>Add degassed methanol (30 ml) and triethylamine (9.5 ml, 68.1 mmol), and stir at RT for 1 hr to ensure conversion of the phosphonium chloride salt to the hydroxymethene phosphine. Next, add degassed ammonia solution in methanol (2 M, 4.1 ml, 8.2 mmol).</li>
	<li>Heat the reaction mixture for 2 hr under reflux, during which the ligand will precipitate out as a white solid.</li>
	<li>Although the N-triphosPh ligand is stable to oxidation in air over short periods of time, for optimal purity, remove the solvent via cannula filtration26 under nitrogen, and rinse with degassed methanol (3 x 10 ml) to obtain an analytically pure product, and store under a nitrogen atmosphere.</li>
</ol>
2. Synthesis of [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2)
<ol>
	<li>To a 200 ml oven dried Schlenk flask, add N-TriphosPh (1.0 g, 1.63 mmol) and [Ru3(CO)12] (347 mg, 0.54 mmol), and place under nitrogen via three sequential vacuum-nitrogen cycles on a dual-manifold Schlenk line.</li>
	<li>Add 30 ml of dry, degassed toluene and bring the mixture to reflux for 12 hr.</li>
	<li>After this 12 hr reflux, filter the solution via cannula to a second Schlenk flask to remove small amounts of metallic ruthenium that form during the course of the reaction.</li>
	<li>Reduce the volume of solvent to approximately 10 ml under vacuum using a dual-manifold Schlenk line fitted with a liquid nitrogen cooled trap, to induce precipitation of the complex.</li>
	<li>Recrystallize the precipitate by heating gently (80&#8211;90 &#176;C) in an oil bath until complete redissolution occurs, and subsequent slow cooling to RT by removing the heat from the oil bath, but allowing the Schlenk flask to remain submerged. Leave O/N to give an orange crystalline solid.</li>
	<li>Isolate the orange crystals suitable for X-ray diffraction via cannula filtration of the supernatant into another oven dried Schlenk flask. Next, rinse the crystals with dry and degassed toluene (2 x 5 ml) and dry in vacuo O/N. Save the combined supernatant and washings in a separate Schlenk flask.</li>
	<li>Obtain a second batch of crystals from the combined supernatant and rinsing solutions by a similar recrystallization process to steps 2.5 and 2.6 to improve the overall yield of reaction.</li>
	<li>Store the complex under nitrogen as exposure to air leads to the slow conversion to the oxidized carbonate complex (see below).</li>
</ol>
3. Synthesis of [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3)
<ol>
	<li>To a 200 ml Schlenk flask, add 2 (280 mg, 0.364 mmol) and 5 ml of toluene to generate a partially dissolved orange suspension.</li>
	<li>Insert a needle attached to a balloon of oxygen into the suspension and bubble oxygen at a rate of 2&#8211;3 bubbles per second through the reaction mixture for 10 min.</li>
	<li>As an orange precipitate forms, collect it by filtration in air and washed with toluene (2 x 5 ml) and diethyl ether (2 x 5 ml) and dry in vacuo to give a free flowing orange powder that was stable in air.</li>
	<li>In order to grow crystals suitable for X-ray diffraction, dissolve 100 mg of 3 in 3 ml dichloromethane in a vial and layer 3 ml toluene on top by slowly allowing this solvent to run down the side of the vial.
	<ol>
		<li>Leave this O/N to obtain crystals. Isolate the crystals by decanting the supernatant, and washing the toluene (2 x 3 ml) and diethyl ether (2 x 3 ml). Dry in vacuo on a dual-manifold Schlenk line.</li>
	</ol>
	</li>
</ol>
4. Synthesis of [Ru(H)2(CO){N(CH2PPh2)3}-&#954;3P] (4)
<ol>
	<li>Prepare a solution of 3 (763 mg, 0.953 mmol) in 20 ml of dry, degassed THF and inject into a 100 ml Autoclave Engineer&#8217;s high-pressure reactor under a positive pressure (0.2 bar) of nitrogen.</li>
	<li>Change the reactor head space gas to 100% hydrogen and pressurize to 15 bar at RT, then heat to 100 &#176;C with stirring for 2 hr. 
	Caution! Ensure all safety procedures have been adhered to when using high pressure systems!</li>
	<li>After cooling to RT, carefully vent the excess hydrogen gas in the reactor head space and change to nitrogen.</li>
	<li>Transfer the reaction solution to a 100 ml Schlenk flask under nitrogen and, after reconnecting to a dual-manifold Schlenk line, filter via cannula and dilute with 20 ml of dry, degassed methanol.</li>
	<li>Remove the solvent under vacuum using a dual-manifold Schlenk line fitted with a liquid nitrogen cooled trap to give an orange powder. Wash this orange powder with dry, degassed methanol (3 x 5 ml) and dry, degassed diethyl ether (3 x 5 ml) and dry in vacuo.</li>
	<li>Grow crystals suitable for X-ray diffraction analysis O/N from a saturated dry and degassed toluene solution of 4 layered with an equivolume amount of dry, degassed methanol.</li>
	<li>Store the complex under nitrogen.</li>
</ol>
5. Reaction of [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4) with NH4PF6 and Levulinic Acid
<ol>
	<li>Prepare a solution of 4 (48.4 mg, 65.2 &#956;mol) in 2 ml dry, degassed toluene in a oven dried Schlenk flask, and add via syringe to a stirred solution of NH4PF6 (10.6 mg, 65.0 &#956;mol) in acetonitrile (2 ml) in a separate oven dried Schlenk flask.</li>
	<li>Stir the reaction mixture at RT for 2 hr. After, remove the solvent in vacuo using a dual-manifold Schlenk line fitted with a liquid nitrogen cooled trap to give the intermediate complex [RuH(CO)(MeCN){N(CH2PPh2)3}-&#954;3P] (5).</li>
	<li>Wash with dry, degassed hexane (3 x 3 ml) and dry in vacuo to isolate complex 5 as a brown powder.</li>
	<li>To a solution of 5 in 0.5 ml degassed acetone-d6, add levulinic acid (10.8 mg, 93.0 &#956;mol, 1.43 equiv.) in 0.5 ml of degassed acetone-d6. Stir the reaction mixture for 2 min using a vortex stirrer.</li>
	<li>Record 1H and 30P{1H} NMR spectra of the reaction every hour for 16 hr to observe the reaction.27</li>
</ol>

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The authors have nothing to disclose.

Herein we have described efficient synthetic procedures for the synthesis of a tridentate phosphine ligand and a series of ruthenium complexes. The N-triphosPh ligand (1) can be easily prepared in high yield with a minimalistic work-up procedure. This phosphorus based Mannich reaction used to synthesize these types of ligands is quite general and can be used for other ligand derivatives with differing R-groups on the P-atoms.10-12,15-18 Additionally, this synthetic methodol...

Ruthenium phosphine based complexes are some of the most widely studied and chemically versatile molecular catalysts.1-9 Typically, such ruthenium catalysts contain either mono- or bi-dentate ligands that dictate the electronics, sterics, geometry and solubility of the complex, and which profoundly impact on catalytic activity. Multidentate phosphine systems have been less widely studied for catalysis, as they are known to impart greater stability on the metal center owing to the greater chelate effect of multiple phosphorus donors on the metal center. Such stabilization can be undesirable for catalysis, however, under harsher reaction conditions (higher temperatures and pressures) the complex stabilizing properties of such ligands can be advantageous in ensuring catalyst integrity. One such multidentate phosphine ligand system that we10-12 and others13-18 have investigated for imparting complex stability and facial coordination geometries is the so-called N-triphos ligand series where three phosphine arms are attached to an apical bridging nitrogen atom forming a potentially tridentate ligand. One of the key features to these particular ligands is the facile way that they can be synthesized via a phosphorus based Mannich reaction from readily available secondary phosphines (Figure 1), hence phosphines with a variety of R-groups can be prepared usually in high yields and with minimal work-up. The overall goal of this methodology is to present a facile route by which ruthenium dihydride complexes featuring N-triphos ligands can be accessed for subsequent catalytic applications. Recently, Ru-triphos based complexes have attracted attention as catalysts for the hydrogenation reactions of biomass derived products, such as levulinic acid,19,20 bio-esters11,21 and carbon dioxide22 to higher value chemicals. It would be advantageous to expand the scope of Ru-triphos derivatives that are either as, or more active than the systems already reported, especially if they are synthetically easier to access, such as the N-triphos ligand. The most studied carbon-centered analogue typically suffers from low yielding synthesis and involves highly air-sensitive metal phosphide reagents, unlike the N-triphos ligand, which is more adaptable and easier to prepare.10-18
N-triphos ligands remain relatively under-investigated, with only molybdenum, tungsten, ruthenium, rhodium and gold complexes having been reported from nine publications. This is in stark contrast to the boron- and carbon-centered analogues, for which there are around 50 and 900 articles, respectively, with a great number of unique compounds. Nonetheless, N-triphos containing complexes have found application in the asymmetric catalytic hydrogenation of pro-chiral olefins23 as well as asymmetric cyclohydroamination of N-protected &#947;-allenyl sulfonamides.24 Additionally, a ruthenium complex coordinated by a bulky N-triphos ligand featuring phospholane coordinating moieties was found to activate silanes, a key step in the development of organosilicon chemistry.25
As part of the ongoing research program in catalysis, we sought to prepare a range of ruthenium N-triphosPh precatalysts and to investigate their stoichiometric reactions and catalytic potential. Despite molybdenum complexes of N-triphosPh having first been reported over 25 years ago, their application, catalytic or otherwise has not been investigated. This work demonstrates the applicability of the N-triphos scaffold, which despite being generally underdeveloped, possess many desirable features such as complex stability. Herein we report the synthetic route and characterization of to a series of ruthenium N-triphosPh complexes that may find application in catalytic hydrogenation reactions.

<table><tbody><tr><td>Methanol</td><td></td><td></td><td>Obtained from in-house solvent purification system: Innovative Technology, inc &quot;pure solv&quot; drying tower. Stored in ampules over activated molecular sieves under nitrogen.</td></tr><tr><td>Toluene</td><td></td><td></td><td></td></tr><tr><td>Diethyl Ether</td><td></td><td></td><td></td></tr><tr><td>Tetrahydrofuran (THF)</td><td></td><td></td><td></td></tr><tr><td>Acetonitrile</td><td></td><td></td><td></td></tr><tr><td>d&lt;sub&gt;6&lt;/sub&gt;-Acetone</td><td>VWR</td><td>VWRC87152.0011</td><td>Store in fridge</td></tr><tr><td>Triethylamine</td><td>Sigma-Aldrich</td><td>TO886-1L</td><td>Distilled and stored over activated molecular sieves under N&lt;sub&gt;2&lt;/sub&gt;</td></tr><tr><td>2 M Ammonia solution in methanol</td><td>Sigma-Aldrich</td><td>341428-100ML</td><td>Solution comes in a &quot;Sure-Seal&quot; bottle</td></tr><tr><td>NH&lt;sub&gt;4&lt;/sub&gt;PF&lt;sub&gt;6&lt;/sub&gt;</td><td>Sigma-Aldrich</td><td>216593-5G</td><td>Store in desiccator</td></tr><tr><td>Levulinic Acid</td><td>Acros Organics</td><td>125142500</td><td>Solid but melts close to room temperature</td></tr><tr><td>3 &amp;Aring; Molecular sieves</td><td>Alfa Aesar</td><td>LO5359</td><td>Activate by heating over night under vacuum</td></tr><tr><td>Schlenk flasks</td><td>GPE</td><td>Custom design</td><td></td></tr><tr><td>Dual-manifold Schlenk line</td><td>GPE</td><td>Custom design</td><td>Dual-manifold of i) N&lt;sub&gt;2&lt;/sub&gt; that has been passed through a silica drying column and ii) vacuum.</td></tr><tr><td>Rotary vacuum pump</td><td>Edwards</td><td>RV3 A652-01-903</td><td></td></tr><tr><td>100 ml Autoclave Engineer&#039;s high pressure reactor</td><td>Autoclave Engineer</td><td>Custon design</td><td></td></tr><tr><td>Vortex Stirrer</td><td>VWR</td><td>444-1378</td><td></td></tr></tbody></table>

the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

The N-triphosPh ligand (1) and the ruthenium complex series: Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2), [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) and [Ru(H)2(CO){N(CH2PPh2)3}-&#954;3P] (4) were characterized via 1H, 13C{1H...

Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

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12.1K Views.  Imperial College London. Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru–N-triphos complex with levulinic acid is described.

Video: The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 &deg;C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. 
The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.

Herein is described the synthesis, isolation, and reactions of hypervalent iodonium alkynyl triflates (HIATs) with azides to generate cyanocarbenes. The procedures will involve air-sensitive and cryogen techniques, including cold filtration under an inert atmosphere. Handling and safety of the synthesized compounds will also be discussed.

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of this compound commences from [Ru(NH3)5Cl]Cl2 in 1 M NH4OH in a closed container, yielding a green solution. Purification is accomplished with cation-exchange chromatography. This compound is characterized and verified to be pure by UV-vis and IR spectroscopy. The mitochondrial calcium uptake inhibitory properties are assessed in permeabilized HeLa cells by fluorescence spectroscopy.

A protocol for the synthesis, purification, and characterization of a ruthenium-based inhibitor of mitochondrial calcium uptake is presented. A procedure to evaluate its efficacy in permeabilized mammalian cells is demonstrated.

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of ...

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile N-(2-alkoxyvinyl)sulfonamides, which react under a variety of conditions to afford useful N- and O-containing compounds. Acid-catalyzed addition of alcohols or thiols to N-(2-alkoxyvinyl)sulfonamide-containing phthalans provides access to ketals and thioketals, respectively. Selective reduction of the vinyl group in N-(2-alkoxyvinyl)sulfonamide-containing phthalans via hydrogenation yields the corresponding phthalan in good yield, whereas reduction with sodium bis(2-methoxyethoxy)aluminumhydride generates a ring-opened phenethylamine analogue. Because the N-(2-alkoxyvinyl)sulfonamide functional group is synthetically versatile, but often hydrolytically unstable, this protocol emphasizes key techniques in preparing, handling, and reacting these pivotal substrates in several useful transformations.

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Representative experimental procedures for the synthesis of N-(2-alkoxyvinyl)sulfonamides and subsequent conversion to phthalan and phenethylamine derivatives are presented in detail.

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile ...

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by Gallium(III) and H3 5,10,15-tris(pentafluorophenyl)corroles

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic macrocycles that exhibit differential cytostatic and cytotoxic properties in specific cell lines, depending on the identities of the chelated metal and functional groups. The unique behavior of functionalized corroles towards specific cell lines introduces the possibility of targeted chemotherapy.
Many anticancer drugs are evaluated by their ability to inhibit RNA transcription. Here we present a step-by-step protocol for RNA transcription in the presence of known and potential inhibitors. The evaluation of the RNA products of the transcription reaction by gel electrophoresis and UV-Vis spectroscopy provides information on inhibitive properties of potential anticancer drug candidates and, with modifications to the assay, more about their mechanism of action.
Little is known about the molecular mechanism of action of corrole cytotoxicity. In this experiment, we consider two corrole compounds: gallium(III) 5,10,15-(tris)pentafluorophenylcorrole (Ga(tpfc)) and freebase analogue 5,10,15-(tris)pentafluorophenylcorrole (tpfc). An RNA transcription assay was used to examine the inhibitive properties of the corroles. Five transcription reactions were prepared: DNA treated with Actinomycin D, triptolide, Ga(tpfc), tpfc at a [complex]:[template DNA base] ratio of 0.01, respectively, and an untreated control.
The transcription reactions were analyzed after 4 hr using agarose gel electrophoresis and UV-Vis spectroscopy. There is clear inhibition by Ga(tpfc), Actinomycin D, and triptolide.
This RNA transcription assay can be modified to provide more mechanistic detail by varying the concentrations of the anticancer complex, DNA, or polymerase enzyme, or by incubating the DNA or polymerase with the complexes prior to RNA transcription; these modifications would differentiate between an inhibition mechanism involving the DNA or the enzyme. Adding the complex after RNA transcription can be used to test whether the complexes degrade or hydrolyze the RNA. This assay can also be used to study additional anticancer candidates.

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by GalliumIII and H3 5,10,15-trispentafluorophenylcorroles

Gallium(III) 5,10,15-(tris)pentafluorophenylcorrole and its freebase analogue exhibit low micromolar cell cytotoxicity. This manuscript describes an RNA transcription reaction, imaging RNA with an ethidium bromide-stained gel, and quantifying RNA with UV-Vis spectroscopy, in order to assess transcription inhibition by corroles and demonstrates a straightforward method of evaluating anticancer candidate properties.

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic ...

Bioengineering

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 ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesH+BPh4-) as the protected form of NHC is employed. IMesH+BPh4- can be obtained in a single step by anion exchange between 1,3-dimesitylimidazolium chloride and sodium tetraphenylborate. A real-time steady-state photolysis setup is described, which hints that the photochemical reaction proceeds in two consecutive steps: 1) ITX triplet is photo-reduced by the borate anion and 2) subsequent proton transfer takes place from the imidazolium cation to produce the expected NHC IMes. Two separate characterization protocols are implemented. Firstly, CS2 is added to the reaction media to evidence the photogeneration of NHC through formation of the IMes-CS2 adduct. Secondly, the amount of NHC released in situ is quantified using acid-base titration. The use of this NHC photo-generating system for the ROMP of norbornene is also discussed. In solution, a photopolymerization experiment is conducted by mixing ITX, IMesH+BPh4-, [RuCl2(p-cymene)]2 and norbornene in CH2Cl2, then irradiating the solution in a UV reactor. In a dispersed medium, a monomer miniemulsion is first formed then irradiated inside an annular reactor to produce a stable poly(norbornene) latex.

We describe a protocol to photogenerate N-heterocyclic carbenes (NHCs) by UV irradiation of a 2-isopropylthioxanthone/imidazolium tetraphenylborate salt system. Methods to characterize the photoreleased NHC and elucidate the photochemical mechanism are proposed. The protocols for ring-opening metathesis photopolymerization in solution and miniemulsion illustrate the potential of this 2-component NHC photogenerating system.

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis (FCLSA) on spectral data, in addition to CIE color coordinate determination and basic spectral processing. While some of the features may be found in commercial software or in programs made by&#160;academic research groups, we believe that ARL Spectral Fitting is the only application that possesses all three of the aforementioned attributes.
This program is intended as a standalone, GUI-based application for use by an average laboratory researcher without requiring any coding knowledge or proprietary software. In addition to the standalone executable hosted on ARL GitHub, the associated MATLAB files are available for use and further development.
FCLSA augments the information found in luminescence spectra, providing meaningful insight into the relationship between the ground and excited states of a photoluminescent species. This insight is achieved by modeling spectra with two versions (modes) of an equation that are characterized by either four or six parameters, depending on which mode is used. Once optimized, the value of each of these parameters can be used to gain insight into the molecule, as well as to perform further analysis (for example, the free energy content of the excited-state molecule). This application provides tools for easy by-hand fitting of imported data, as well as two methods for optimizing this fit-damped least-squares fitting, powered by the Levenberg-Marquardt algorithm, and derivative-free fitting utilizing the Nelder-Mead simplex algorithm. Furthermore, estimations of sample color can be performed and reported in CIE and RGB coordinates.

This protocol introduces Franck-Condon Lineshape Analyses (FCLSA) of emission spectra and serves as a tutorial for the use of ARL Spectral Fitting software. The open-source software provides an easy and intuitive way to perform advanced analysis of emission spectra including excited state energy calculations, CIE color coordinate determination, and FCLSA.

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis ...

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

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Chapters in this video

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Synthesis of a Water-soluble Metal–Organic Complex Array

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by Gallium(III) and H₃ 5,10,15-tris(pentafluorophenyl)corroles

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

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis