The authors would like to thank the National Science Foundation for the continuous financial support (CHE-0742365) and for the purchase of a Bruker APEX II diffractometer (CHE-0443233) and a Bruker Microtof-II mass spectrometer (CHE-0741793). The authors would also like to thank CEST facility for their use of the Micromass Quattro-LC mass spectrometer.

1. Preparing Niobium Tubes
<ol>
 <li>Before cutting the niobium (Nb) tubes, prepare Nb-cleaning solution. In a 500 ml plastic bottle, measure out and add via a 100 ml measuring cylinder the following stock solutions as received: 110 ml H2SO4, followed by 50 ml HNO3, followed by 40 ml HF. Mix well and allow reaching room temperature before using.</li>
 <li>Measure the Nb tube, 4.5 cm in length, and cut with a pipe cutter. Avoid kinking the tubing. Repeat 3 more times.</li>
 <li>In a well-ventilated fume-hood, place the four Nb tubes, length-wise, in a 100 ml plastic beaker. Pour the Nb-cleaning solution into the beaker until tubes are completely covered. Close the sash of the fume-hood. Wait 12 to 20 seconds, or until brown nitrous oxide gas is released. Immediately fill the beaker with water and allow reaching room temperature.</li>
 <li>Use plastic thongs to remove Nb tubes, wash several times with water and then acetone, and dry them in a high temperature drying oven. (Dispose of the used acid solution after carefully neutralizing with KOH).</li>
 <li>Take the Nb tubes out of the oven and allow cooling down to room temperature. With vise-grips crimp about 1 cm of one end of each tube. Bend slightly the edge, about 1 mm.</li>
 <li>Turn on the vacuum pump and argon gas cylinder of the arc-welder. Clamp the four Nb tubes, in a staggered position, in the arc-welder's holder. Center the brass block (heat sink) in the arc-welder and slowly adjust niobium tubes on top. Close and clamp shut the door of arc welder.</li>
 <li>Adjust welding tip to height of niobium tubes. Turn on vacuum valve (ensure that argon refill valve is close). Allow vacuum to reach below 100 mm Hg (ideal: 30 mm Hg; wait time: 30 - 40 minutes) in order to completely evacuate chamber and Nb tubes of all air and moisture.</li>
 <li>When 30 - 60 mm Hg vacuum is achieved, close vacuum valve and slowly open the valve to argon cylinder to refill with argon to 7 in. Hg. Close argon gas valve. System should now be under partial vacuum.</li>
 <li>Put on certified rubber welding gloves. Position protective welding darkened glass over the window of the arc welder. Turn on the source set at 15 A (thicker niobium tubes use 20 - 55 A). As welding tip makes contact with niobium tube, welding arc forms, raise 1 cm over tube and slowly sweep above tube as niobium melts and seals completely. Repeat for remaining niobium tubes. Turn off power source and allow system to reach room temperature (15 - 30 min).</li>
 <li>Remove clamp from arc welder door. Slowly open argon gas valve and refill with argon until door is opened.</li>
 <li>Remove niobium tubes and label with electrical engraver: A, B, C, and D, respectively. Place back in drying oven until dry and place hot in antechamber of drybox, pumping under vacuum for 30 - 45 min.</li>
 <li>Refill small antechamber with high-purity nitrogen/argon gas. Bring four labeled niobium tubes into drybox. The containers are now ready to be loaded.</li>
</ol>
2. Loading Niobium Tubes: Preparing K4Ge9
<ol>
 <li>Tare the balance and then measure 156 mg K (4 mmol). With a spatula, carefully insert it into the Nb tube and push to the bottom.</li>
 <li>Weigh 653 mg of Ge (9 mmol) and insert into the tube on top of potassium metal.</li>
 <li>Carefully crimp the open end of the Nb tube using vise-grips and slightly bend the edge. Repeat for the three other Nb tubes. Place all four tubes in a jar [under inert gas], close the jar and place it in the box antechamber in order to bring out.</li>
 <li>Following steps 1.5 - 1.8, weld edges of four Nb tubes. The loaded tubes are now ready to be sealed in a fused silica tube.</li>
</ol>
3. Preparing Fused Silica Tube via Glass-Blowing
<ol>
 <li>Use circular glass saw to cut 10-14" pieces of large quartz tube (ID/OD = 20/22 mm) and medium quartz tube (7/9 mm). Cut also end of round ball joint. Wash thoroughly with water and acetone. Place in glass drying oven until completely dry. Take out of oven and allow reaching room temperature.</li>
 <li>Light the hydrogen/oxygen torch with a striker and slowly increase oxygen flow to get hot blue flame. Put on darkened safety glasses before inserting any quartz tubing into flame.</li>
 <li>Insert the large tube in the flame and slowly rotate one end allowing the tube to collapse to a bottle neck and then completely close. Using a spare medium quartz tube as a shaping rod, pull one end of the "white hot" (as seen through safety glasses) quartz tube to close the opening more quickly.</li>
 <li>After sealing opening, attach rubber septum with a blow hose at the open end and insert blow pipe into mouth (do not blow yet). While rotating the sealed end in the flame, slightly blow to keep positive pressure and prevent glass from collapsing. Next, a small hole is ready to be made in the center.</li>
 <li>Adjust gas flow to create a sharp blue flame and focus flame in center of closed end. When targeted spot becomes white hot, blow hard to create a large bubble or opening. Break bubble by gently scraping on lab bench. Insert opened hole into flame and open to 0.7 - 1cm while flaring edges with graphite reamer. This part (body) is now ready to be attached to the smaller tubing (neck).</li>
 <li>Close one end of the neck piece with rubber septum. Holding in one hand the body (with mouthpiece in mouth, be ready to blow) and in other hand the neck slowly rotate both ends simultaneously in the flame. Attach the ends and straighten outside of flame.</li>
 <li>Adjust size of flame to sharp one and slowly work out each quarter of sealed joint to ensure no holes and air bubbles. Keep positive pressure in order to prevent glass from collapsing. Remove the septum from top of neck. The neck is now ready to be attached to the ball joint.</li>
 <li>Using septum, close ball joint opening. Attach end of ball joint to neck following steps 3.5 - 3.6.</li>
 <li>Insert four Nb tubes into opened end of body. Attach end of blow hose to ball joint. Slowly close opened end of body by following step 3.3. Turn off flame and close all gas cylinders. Allow fused silica/quartz jacket to cool down.</li>
 <li>Pour dilute Nb cleaning solution (2 H20: 1 solution, refer to 1.1) into the silica tube and keep for 3 - 5 minutes until the Nb tubes are shiny and free of any oxidized areas. Rinse three times each with distilled water and acetone. Allow to dry completely. The niobium tubes are now in a fused silica/quartz jacket and ready to be evacuated and sealed off.</li>
</ol>
4. Sealing Fused Silica Tube using a High Vacuum Line
<ol>
 <li>Turn on the pump for the vacuum line. Fill dewars with liquid nitrogen. Turn on the mercury diffusion pump and the cooling water. Allow to reflux for a minimum of 30 minutes.</li>
 <li>Coat ball joint of fused silica jacket with high vacuum silicone grease. Attach to vacuum line. Evacuate tube completely for 30 min.</li>
 <li>Using a tesla coil, check for any leaks/holes.</li>
 <li>Put on Borosilicate Safety Glasses. Turn on small house gas/oxygen torch. Slowly pass flame from bottom of tube to neck, ensuring all air and moisture is gone.</li>
 <li>Slowly pass flame over Nb tubes, heating gently for 1 - 2 minutes. Careful not to get glass white hot as it will collapse as it is pulled in by high vacuum. Turn off torch and allow fused silica jacket to reach room temperature (15 - 30 min).</li>
 <li>Repeat step 4.4. Intensify flame to a sharp hot blue color. Slowly seal off tube below ball and neck joint. (Tip: can get entire glass area white hot and assist by slowing pulling off with other hand by holding end of silica jacket). Turn off torch.</li>
 <li>Turn off Hg-distillation. Allow to reach room temperature. Turn off water. Allow liquid nitrogen to slowly evaporate. The fused silica jacket is now ready to be placed in the furnace.</li>
</ol>
5. Heating the Reaction Mixtures in a Furnace
<ol>
 <li>Gently bring niobium tubes to center of quartz jacket and place directly over thermocouple. Insulate openings of furnace with glass wool. Turn on furnace and set at 950 &deg;C for two days.</li>
 <li>After completion, using the glass-cutting circular saw (refer to 3.1) cut open the end of the fused silica tube and remove the Nb containers. Wash the niobium free of any debris with water and acetone and dry in the oven. Pump into the drybox.</li>
 <li>Using wire-cutting pliers cut the ends of the niobium tubes. Gently crush the coarse product. The fine intermetallic precursor is now ready to be brought into solution.</li>
</ol>
6. Dissolving Precursor in Ethylenediamine
<ol>
 <li>Weigh out 81 mg (0.1 mmol) of K4Ge9 into a test-tube. Add stir bar.</li>
 <li>Pipette in 2 - 2.5 ml of anhydrous ethylenediamine (previously distilled over sodium metal) and stir for 5 - 10 min at room temperature. A bright red solution forms.</li>
 <li>Note: If solution is stirred for too long, it will become green, indicative of oxidized clusters. A red solution is desired for functionalization.</li>
</ol>
7. Reacting Ge9-clusters with Me3SiC&equiv;CSiMe3
<ol>
 <li>Slowly syringe in, drop-wise, 0.056 ml (0.25 mmol; a little over 2 equivalents) of Me3SiC&equiv;CSiMe3. Oily layer is seen on top of the red cluster solution. As the reaction is stirred, the solution slowly becomes brown. Stir for four hours until a clear honey-brown solution is achieved.</li>
 <li>Place test-tube in centrifuge for 15 min. Carefully remove. Insert a glass fiber filter pipette (previously packed, dried at 180 &deg;C overnight and pumped into drybox) into a clean test-tube.</li>
 <li>Carefully pipette the supernatant solution into the filter pipette and allow to filter. The clear honey-brown filtrate is now collected.</li>
 <li>Set aside 0.1 ml of filtrate in order to run an electrospray mass spectrometry (ES-MS) sample to confirm product before crystallization.</li>
</ol>
8. Running ES-MS of Reaction Solution
<ol>
 <li>Pump a clean 1 ml Hamilton syringe, syringe plunger and PEEK tubing into antechamber of drybox, for at least 30 - 45 min.</li>
 <li>Insert syringe plunger into syringe and fill with anhydrous ethylenediamine and dispense into a waste container. Purge the syringe two more times.</li>
 <li>Fill the syringe again with anhydrous ethylenediamine and push through the PEEK tubing. Purge the PEEK tubing two more times. The PEEK tubing is now filled with anhydrous ethylenediamine.</li>
 <li>Fill the empty syringe with the filtered Ge9-divinyl solution. (Tip: this can be placed in a nitrogen filled Ziploc bag for transportation if mass spectrometer is outside of the drybox). Bring out of drybox.</li>
 <li>Place syringe attached to PEEK tubing in Harvard syringe pump at 10 &mu;L/min. Attach PEEK tubing securely to electrospray mass spectrometer. Collect spectrum in the negative ion mode on a Micromass Quattro-LC triple quadrupole mass spectrometer (typical conditions: 100 &deg;C source temperature, 125 &deg;C desolvation temperature, 2.5 kV capillary voltage, 30 - 65 V cone voltage) or on a Bruker Microtof-II mass spectrometer (capillary at 3800 V, nebulizer at 0.6 Bar, desolvation temperature at 190 &deg;C, capillary exit at 100 V, detector at 1200 V). (Note: samples are highly air and moisture sensitive, purging the chamber for 15 - 60 min before running samples is preferred.)</li>
 <li>Resulting spectrum will show isotope pattern for the functionalized clusters (see Figure 1). The remaining filtrate in the drybox can now be crystallized.</li>
</ol>
9. Crystallizing Ge9-divinyl Ions with a Sequestering Agent
<ol>
 <li>Pipette remaining filtrate into two equal aliquots in two clean test-tubes. Label test-tubes C and D (as an example). Set aside.</li>
 <li>Weigh 0.4 mmol (105 mg) of anhydrous 18-crown-6 into a clean test-tube and add 8 ml of toluene. Mix well until completely dissolved.</li>
 <li>Layering with Toluene, Method A: Gently pipette 4 ml of this solution on top of the test-tube C and D. (Tip: Try to achieve two separate phases.) Place a rubber stopper on each test-tube. Set aside undisturbed in a test-tube rack to crystallize.</li>
 <li>Layering with Toluene, Method B: Pipette 4ml of 18-crown-6/toluene solution into two clean test-tube labeled E and D. Insert a filter pipette (note: if solution needs to be filtered again) or a regular pipette into test-tube E and F. Pipette the solution of test-tube C into E and test-tube D into F. (Note: this reverse layering will quickly result in two phases.) Place a rubber stopper on each test-tube. Set aside undisturbed in a test-tube rack to crystallize.</li>
 <li>Bright orange blocks should crystallize within 1 - 3 days. The unit cell of the crystals can then be confirmed by single crystal X-ray diffraction.</li>
</ol>
10. Checking Crystals Unit Cell on a D8-Diffractometer
<ol>
 <li>Fill a plastic bottle with Paratone-N oil and allow all air bubbles to be removed. Completely degas the oil in antechamber of drybox, under vacuum, overnight. Bring into the drybox.</li>
 <li>Apply 2 - 3 drops to glass slide. Coat spatula tip in the oil and insert into crystallizing test-tube. Select orange crystals from the test-tube and immersed in the Paratone-N oil. (Note: ensure all air-sensitive crystals are coated in oil). Bring outside drybox.</li>
 <li>Using a high resolution microscope, select a single crystal and drag to the edge of the oil on the slide with a straight stainless probe.</li>
 <li>Carefully remove excess oil from the crystal by dragging to edge of glass slide. Mount single crystal on Mitegen micro mount loop and quickly position under cold stream (100 K) of the Bruker D8 APEX-II diffractometer equipped with CCD area detector using graphite-monochromated Mo K&alpha; radiation.</li>
 <li>Ensure good high angle diffractions and acquire unit cell.</li>
 <li>Compare and confirm unit cell to that of [K(18-crown-6)]2[Ge9(HCCH2)2]&bull;en, 1, triclinic, P-1, a = 10.974(4), b = 14.3863(5), and c = 16.2272(6) &Aring;, &alpha; = 85.946(2), &beta; = 71.136(2), and &gamma; = 89.264(2) &deg;, V = 2412.21(15) &Aring;3, Z =2. 53</li>
</ol>
11. Representative Results
The unique isotope pattern of the anionic clusters allows them to be easily detected in the negative ion-mode (Fig 1). Also noteworthy is that reduced singly charged species, in addition to pairing with a potassium ion is a common phenomenon of this soft-ionization technique.59
The crystal structure with relevant bond lengths and angles of [Ge9(CH=CH2)2]2- in [K(18-crown-6)]2[Ge9(HCCH2)2]&bull;en, 1, can be seen in Figure 2 .
<img alt="Figure 1" src="/files/ftp_upload/3532/3532fig1.jpg" /> 
Figure 1. ES-MS spectra (negative-ion mode) of ethylenediamine solutions of the reactions of Ge9 clusters with Me3SiC&equiv;CSiMe3. Shown are also the theoretical isotope distributions below the experimental distribution. (Sevov et. al. Inorg. Chem. 2007, 46, 10953.)
<img alt="Figure 2" src="/files/ftp_upload/3532/3532fig2.jpg" /> 
Figure 2. A view of [K(18-crown-6)]2[Ge9(HCCH2)2]&bull;en, 1. Color scheme: <img alt="Bullet 1" src="/files/ftp_upload/3532/3532bullet1.jpg" /> = Ge, <img alt="Bullet 2" src="/files/ftp_upload/3532/3532bullet2.jpg" /> = C, <img alt="Bullet 3" src="/files/ftp_upload/3532/3532bullet3.jpg" /> = H. Selected bond lengths and angles: Ge-C 1.961 and 1.950 &Aring;, C=C 1.318 and 1.316 &Aring;, Ge-C-C 123 and 127 &deg;. (Sevov et. al. Inorg. Chem. 2007, 46, 10953.)
<img alt="Figure 3" src="/files/ftp_upload/3532/3532fig3.jpg" /> 
Figure 3. Schematic representation of Preparing Niobium Tubes: (a) cutting Nb tubes; (b) cleaning Nb tubes in a Nb acid solution; (c) using vise-grips to crimp and bend Nb tube.
<img alt="Figure 4" src="/files/ftp_upload/3532/3532fig4.jpg" /> 
Figure 4. Schematic representation of Preparing Niobium Tubes: (a) diagram of arc welder; (b) staggered Nb tubes in arc welder holder and (c) welding tip above Nb tubes.
<img alt="Figure 5" src="/files/ftp_upload/3532/3532fig5.jpg" /> 
Figure 5. Schematic representation of Loading Niobium Tubes : (a) inside the drybox and (b) Nb tubes: (i) before welding, (ii) after using vise-grips to crimp one edge, (iii) after welding one edge, (iv) after loading and then welding the Nb tube closed, (v) after opening the Nb tube to take out the K4Ge9 precursor.
<img alt="Figure 6" src="/files/ftp_upload/3532/3532fig6.jpg" /> 
Figure 6. Schematic representation of Preparing Fused-Silica Tube by Glass-Blowing in (a) and (b)(i) large and small quartz tubing, (ii) body and neck sealed together, (iii) neck with ball joint, (iv) neck and ball joint sealed together, (v) Nb tubes sealed inside quartz tube, (vi) after the fused silica tube is sealed.
<img alt="Figure 7" src="/files/ftp_upload/3532/3532fig7.jpg" /> 
Figure 7. Schematic representation of Sealing Fused Silica Tubes on a High Vacuum Line in (a) and (b) after the Nb tubes is sealed showing etching of the quartz tube from Nb acid solution.
<img alt="Figure 8" src="/files/ftp_upload/3532/3532fig8.jpg" /> 
Figure 8. Schematic representation of Placing Loaded Fused Silica Tubes in Furnace.
<img alt="Figure 9" src="/files/ftp_upload/3532/3532fig9.jpg" /> 
Figure 9. Schematic representation of Reacting K4Ge9 with Me3SiC&equiv;CSiMe3 inside the drybox (a) (i) unopened Nb tube, (ii) one edge of the Nb tube cut with the (iii) cutting pliers, (iv) crushed precursor and (b) (i) precursor dissolved in ethylenediamine, (ii) immediately after Me3SiC&equiv;CSiMe3 is added (oily droplets on top of test-tube walls seen).
<img alt="Figure 10" src="/files/ftp_upload/3532/3532fig10.jpg" /> 
Figure 10. Schematic representation of Running ES-MS of Reaction Solution in (a) mass spectrometer syringe prepared in dry box, (b) Bruker Microtof-II.
<img alt="Figure 11" src="/files/ftp_upload/3532/3532fig11.jpg" /> 
Figure 11. Schematic representation of Crystallizing Ge9-divinyl with Sequestering Agents in (a) reverse layering and (b) several hours later.
<img alt="Figure 12" src="/files/ftp_upload/3532/3532fig12.jpg" /> 
Figure 12. Schematic representation of Checking Crystals Unit Cell on a D8-Diffractometer: (a) selecting crystals under the microscope and (b) collecting a unit cell.

No conflicts of interest declared.

It is important to clean well the partially oxidized Nb tubes. However, if the tubes are left too long in the Nb cleaning solution, this will severely compromise the thickness of the tube. Thus, 10 &#x2013; 15 seconds are imperative and the tubes should be very lustrous at the end (Fig 3). After the tubes are sealed inside the fused silica jacket they should be cleaned again with a dilute Nb acid solution. This should result in mild effervescence, cleaning any oxidized areas on Nb tubes that occurred during welding o...

<table><tbody><tr><td>D8-Xray diffractometer</td><td>Bruker Corporation</td><td>Bruker APEX II</td><td></td></tr><tr><td>Electrospray mass spectrometer</td><td>Bruker Corporation</td><td>Microtof-II</td><td> </td></tr><tr><td>Electrospray mass spectrometer</td><td>Micromass</td><td>Quattro-LC</td><td>triple -quadropole</td></tr><tr><td>Drybox</td><td>Innovative Technology</td><td>S-1-M-DL</td><td>IT-Sys1 model</td></tr><tr><td>Inert Gas/Vacuum Shielded Arc Welding Arrangement</td><td><a href="http://www.ldsvacuum.com" target="_blank"><img src="/img/new_window.png" /> LDS Vacuum Products</a></td><td>Special Order</td><td></td></tr><tr><td>Arc Welder Power Source</td><td>Miller</td><td>Maxstar-91</td><td> </td></tr><tr><td>Welding Rubber Gloves</td><td>Home Depot</td><td>KH643</td><td> </td></tr><tr><td>Electric Engraver</td><td>Burgess Products</td><td>74</td><td>Vibro-Graver</td></tr><tr><td>Circular Glass Saw</td><td>Pistorius Machine Co. Inc</td><td>GC-12-B</td><td> </td></tr><tr><td>Tube Furnace</td><td>Lindberg/Blue M</td><td>TF55035</td><td>Minimite Laboratory Tube Furnace, Moldatherm (1100 &amp;#x00B0;C)</td></tr><tr><td>Glass Drying Oven</td><td>Fisher Scientific</td><td>13-247-650G</td><td> </td></tr><tr><td>High Vacuum Hg Schlenk-Line</td><td>Special Order</td><td>Univ Of Notre Dame</td><td>Alternative: Edwards E050/60; VWR International; Cat. No. EVB302-07-110</td></tr><tr><td>Large Torch</td><td>Victor Technologies</td><td>JT100C</td><td>Welding torch, tip: Victor 5-W-J </td></tr><tr><td>Small Torch</td><td>Veriflo Co.</td><td>3A</td><td>Blow-pipe </td></tr><tr><td>Tesla Coil</td><td>VWR international</td><td>KT691550-0000</td><td>Leak detector</td></tr><tr><td>Stirrer/Hot -Plate</td><td>VWR international</td><td>12620-970</td><td>VWR HOT PLATE STR DY-DUAL120V</td></tr><tr><td>Balance</td><td>Denver Instrument</td><td>100A</td><td>XE Series</td></tr><tr><td>Centrifuge</td><td>LW Scientific, Inc.</td><td>E8C-08AV-1501</td><td>Variable speed</td></tr><tr><td>Graphite Reamer, (flaring)</td><td>ABR Imagery, Inc.</td><td>850-523 B01</td><td>Open holes in Glass Blowing and flaring edges</td></tr><tr><td>Striker</td><td>Fisher Scientific</td><td>12-007</td><td> </td></tr><tr><td>Vise-Grips</td><td>Home Depot</td><td>0902L3SM</td><td> </td></tr><tr><td>Pipe-Cutter</td><td>Home Depot</td><td>32820</td><td> </td></tr><tr><td>Cutting Pliers</td><td>Home Depot</td><td>437</td><td> </td></tr><tr><td>Plastic Beaker</td><td>VWR international</td><td>13890-046</td><td> </td></tr><tr><td>Measuring Cylinder</td><td>VWR international</td><td>65000-006</td><td>Careful, HF etches glass (if using a glass one)</td></tr><tr><td>Large Plastic Bottle</td><td>VWR international</td><td>16128-542</td><td> </td></tr><tr><td>13 x 100 Test-Tubes</td><td>VWR international</td><td>47729-572</td><td>CULTURE TUBE 13X100 CS1000</td></tr><tr><td>Laboratory (Rubber) Stoppers</td><td>Sigma-Aldrich</td><td>Z164437-100EA</td><td>Size 00</td></tr><tr><td>Test-Tube Rack</td><td>VWR international</td><td>60196-702</td><td>10-13 mm tube OD</td></tr><tr><td>Stir-Bars</td><td>StirBars.com/Big Science Inc.</td><td>SBM-0803-MIC</td><td>PTFE 8x3 mm Micro</td></tr><tr><td>Glass Pipettes</td><td>VWR international</td><td>14673-043</td><td>VWR PIPET PASTEUR 9IN CS1000</td></tr><tr><td>Rubber Bulbs</td><td>VWR international</td><td>56311-062</td><td>Latex, thin walled</td></tr><tr><td>Glass Wool</td><td>Unifrax I LLC</td><td>6048</td><td>Fiberfrax Bulk Fiber Insulation, Ceramic fiber</td></tr><tr><td>Glass Slides</td><td>VWR international</td><td>16004-422</td><td>75x25x1mm, Microscope Slides</td></tr><tr><td>Paratone-N oil</td><td>Hampton Research</td><td>Parabar 10312</td><td>Known as: Paratone-N, Paratone-8277, Infineum V8512</td></tr><tr><td>High Vacuum Silicone Grease</td><td>VWR international</td><td>59344-055</td><td>Dow Corning</td></tr><tr><td>Liquid Nitrogen</td><td>University of Notre Dame</td><td></td><td> </td></tr><tr><td>Argon Gas Cylinder</td><td>Praxair, Inc.</td><td>TARGHP</td><td> </td></tr><tr><td>Nitrogen Gas Cylinder</td><td>Praxair, Inc.</td><td>QNITPP</td><td> </td></tr><tr><td>Oxygen Gas Cylinder</td><td>Praxair, Inc.</td><td>OT</td><td>337 cf CYL</td></tr><tr><td>Hydrogen Gas Cylinder</td><td>Praxair, Inc.</td><td>HK</td><td>195 cf CYL</td></tr><tr><td>Propane Gas Cylinder/source</td><td>University of Notre Dame</td><td>UND</td><td> </td></tr><tr><td>Quartz tubing, Lg</td><td>Quartz Scientific Inc.</td><td>100020B</td><td>20 mm id x 22mm od x 48&quot; clear fused quart tubing</td></tr><tr><td>Quartz tubing, Md</td><td>Quartz Scientific Inc.</td><td>100007B</td><td>Clear Fused Quartz Tubing,7mm id x 9mm od x 48&quot;</td></tr><tr><td>Round Bottom Quartz Joint</td><td>Quartz Scientific Inc.</td><td>6160189B</td><td>Ball joint</td></tr><tr><td>Quartz Safety Glasses</td><td>Wale Apparatus</td><td>11-1127</td><td>waleapparatus.com</td></tr><tr><td>Pyrex Safety Glasses</td><td>Wale Apparatus</td><td>11-2125-B3</td><td>For clear and color borosilicate glass</td></tr><tr><td>Blow Hose Kit</td><td>Glass House</td><td>BH020</td><td>glasshousesupply.com</td></tr><tr><td>Niobium Tubes</td><td>Shaanxi Tony Metals Co., Ltd</td><td>Niobium Tube, 50 ft</td><td>Seamless Niobium Tube Outside diameter: 0.375 (&amp;#177;0.005) inches.&lt;br/&gt; Wall thickness: 0.02(&amp;#177;0.003) Inches Niobium should be annealed.</td></tr><tr><td>PEEK Starter Kit for Mass Spect</td><td>Waters</td><td>PSL613321</td><td>PEEK (PolyEtherEtherKetone) tubing, nuts, ferrule, fits</td></tr><tr><td>Mass Spect Needle Set</td><td>VWR international</td><td>60373-992</td><td>Hamilton Manufacturer (81165)</td></tr><tr><td>H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;</td><td>VWR international</td><td>BDH3072-2.5LG</td><td>ACS Grade</td></tr><tr><td>HNO&lt;sub&gt;3&lt;/sub&gt;</td><td>VWR international</td><td>BDH3046-2.5LPC</td><td>ACS Grade</td></tr><tr><td>HF</td><td>VWR international</td><td>BDH3040-500MLP</td><td>ACS Grade</td></tr><tr><td>Distilled Water</td><td>University of Notre Dame</td><td>UND</td><td> </td></tr><tr><td>Acetone</td><td>VWR international</td><td>BDH1101-4LP</td><td> </td></tr><tr><td>Ethylenediamine</td><td>VWR international</td><td>AAA12132-0F</td><td>99% 2.5 L</td></tr><tr><td>Toluene</td><td>VWR international</td><td>200004-418</td><td>99.8 %, anhydrous</td></tr><tr><td>Mercury</td><td>Strem Chemicals, Inc.</td><td>93-8046</td><td> </td></tr><tr><td>Potassium (K) metal</td><td>Strem Chemicals, Inc.</td><td>19-1989</td><td>Sealed in glass ampoule under Ar</td></tr><tr><td>Germanium (Ge) powder</td><td>VWR international</td><td>AA10190-18</td><td>GERM PWR -100 MESH 99.999% 50G</td></tr><tr><td>Bistrimetylsilylacetylene, (Me&lt;sub&gt;3&lt;/sub&gt;SiC&amp;#8801;CCSiMe&lt;sub&gt;3&lt;/sub&gt;)</td><td>Fisher Scientific</td><td>AC182010100</td><td> </td></tr><tr><td>18-crown-6 (1,4,7,10,13,16-Hexaoxacyclooctadecane)</td><td>VWR international</td><td>200001-954</td><td>99%, 25 gm</td></tr><tr><td>2,2,2-crypt (4,7,13,16,21,24-Hexaoxa-1,10 diazabicyclo[8.8.8]hexacosane)</td><td>Sigma-Aldrich</td><td>291110-1G</td><td>98%</td></tr></tbody></table>

synthesis of nine-atom deltahedral zintl ions of germanium and their functionalization with organic groups

Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 
This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC&equiv;CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left undisturbed for a few days, the so-layered solutions produced orange crystalline blocks of [K(18-crown-6)]2[Ge9(HCCH2)2]&bull;en which were characterized by single-crystal X-ray diffraction. 
The process highlights standard reaction techniques, work-up, and analysis towards functionalized deltahedral Zintl clusters. It is hoped that it will help towards further development and understanding of these compounds in the community at large.

Watch this Scientific Journal Video about Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups at JoVE.com

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

We present the high-temperature synthesis of intermetallic precursors K4Ge9, their dissolution in ethylenediamine to form Ge94- deltahedral Zintl ions, and the reaction of the clusters with alkynes to form organo-Zintl ions. The latter are characterized by electrospray mass spectrometry in solutions and by single-crystal X-ray diffraction in the solid state.

Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 ...

synthesis-nine-atom-deltahedral-zintl-ions-germanium-their

Research

JoVE Journal

Biology

13.9K Views.  University of Notre Dame. We present the high-temperature synthesis of intermetallic precursors K4Ge9, their dissolution in ethylenediamine to form Ge94- deltahedral Zintl ions, and the reaction of the clusters with alkynes to form organo-Zintl ions. The latter are characterized by electrospray mass spectrometry in solutions and by single-crystal X-ray diffraction in the solid state.

Video: Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

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 ...

Chemistry

Soft Lithographic Functionalization and Patterning Oxide-free Silicon and Germanium

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a stable interface that permits efficient electron transport and protects underlying substrates from oxidative degradation. Group IV semiconductors can be effectively protected with highly-ordered self-assembled monolayers (SAMs) composed of simple alkyl chains that act as impervious barriers to both organic and aqueous solutions. Simple alkyl SAMs, however, are inert and not amenable to traditional patterning techniques. The motivation for immobilizing organic molecular systems on semiconductors is to impart new functionality to the surface that can provide optical, electronic, and mechanical function, as well as chemical and biological activity. 
Microcontact printing (&mu;CP) is a soft-lithographic technique for patterning SAMs on myriad surfaces.1-9 Despite its simplicity and versatility, the approach has been largely limited to noble metal surfaces and has not been well developed for pattern transfer to technologically important substrates such as oxide-free silicon and germanium. Furthermore, because this technique relies on the ink diffusion to transfer pattern from the elastomer to substrate, the resolution of such traditional printing is essentially limited to near 1 &mu;m.10-16
In contrast to traditional printing, inkless &mu;CP patterning relies on a specific reaction between a surface-immobilized substrate and a stamp-bound catalyst. Because the technique does not rely on diffusive SAM formation, it significantly expands the diversity of patternable surfaces. In addition, the inkless technique obviates the feature size limitations imposed by molecular diffusion, facilitating replication of very small (&lt;200 nm) features.17-23 However, up till now, inkless &mu;CP has been mainly used for patterning relatively disordered molecular systems, which do not protect underlying surfaces from degradation.
Here, we report a simple, reliable high-throughput method for patterning passivated silicon and germanium with reactive organic monolayers and demonstrate selective functionalization of the patterned substrates with both small molecules and proteins. The technique utilizes a preformed NHS-reactive bilayered system on oxide-free silicon and germanium. The NHS moiety is hydrolyzed in a pattern-specific manner with a sulfonic acid-modified acrylate stamp to produce chemically distinct patterns of NHS-activated and free carboxylic acids. A significant limitation to the resolution of many &mu;CP techniques is the use of PDMS material which lacks the mechanical rigidity necessary for high fidelity transfer. To alleviate this limitation we utilized a polyurethane acrylate polymer, a relatively rigid material that can be easily functionalized with different organic moieties. Our patterning approach completely protects both silicon and germanium from chemical oxidation, provides precise control over the shape and size of the patterned features, and gives ready access to chemically discriminated patterns that can be further functionalized with both organic and biological molecules. The approach is general and applicable to other technologically-relevant surfaces.

Here we describe a simple method for patterning oxide-free silicon and germanium with reactive organic monolayers and demonstrate functionalization of the patterned substrates with small molecules and proteins. The approach completely protects surfaces from chemical oxidation, provides precise control over feature morphology, and provides ready access to chemically discriminated patterns.

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a ...

Bioengineering

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

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 ...

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that derive from initial 2-bromo-2-butene lithiation followed by acid mediated dienol cyclization. The revised synthesis and purification of the ligand avoids the use of mechanical stirring while still permitting access to significant quantities (39 g) of Cp*H in good yield (58%). The procedure offers other additional benefits, including a more controlled quench of excess lithium during the production of the intermediate heptadienols and a simplified isolation of Cp*H of sufficient purity for metallation with transition metals. The ligand was subsequently used to synthesize [Cp*MCl2]2 complexes of both iridium and ruthenium to demonstrate the utility of the Cp*H prepared and purified by our method. The procedure outlined herein affords substantial quantities of a ubiquitous ancillary ligand support used in organometallic chemistry while minimizing the need for specialized laboratory equipment, thus providing a simpler and more accessible entry point into the chemistry of 1,2,3,4,5-pentamethylcyclopentadiene.

Reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented. The revised protocol for the synthesis and purification of the ligand minimizes the need for specialized laboratory equipment while simplifying reaction workups and product purification. Use of Cp*H in the synthesis of [Cp*MCl2]2 complexes (M = Ru, Ir) is also described.

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Staining of Proteins in Gels with Coomassie G-250 without Organic Solvent and Acetic Acid

In classical protein staining protocols using Coomassie Brilliant Blue (CBB), solutions with high contents of toxic and flammable organic solvents (Methanol, Ethanol or 2-Propanol) and acetic acid are used for fixation, staining and destaining of proteins in a gel after SDS-PAGE. To speed up the procedure, heating the staining solution in the microwave oven for a short time is frequently used. This usually results in evaporation of toxic or hazardous Methanol, Ethanol or 2-Propanol and a strong smell of acetic acid in the lab which should be avoided due to safety considerations. In a protocol originally published in two patent applications by E.M. Wondrak (US2001046709 (A1), US6319720 (B1)), an alternative composition of the staining solution is described in which no organic solvent or acid is used. The CBB is dissolved in bidistilled water (60-80mg of CBB G-250 per liter) and 35 mM HCl is added as the only other compound in the staining solution. The CBB staning of the gel is done after SDS-PAGE and thorough washing of the gel in bidistilled water. By heating the gel during the washing and staining steps, the process can be finished faster and no toxic or hazardous compunds are evaporating. The staining of proteins occurs already within 1 minute after heating the gel in staining solution and is fully developed after 15-30 min with a slightly blue background that is destained completely by prolonged washing of the stained gel in bidistilled water, without affecting the stained protein bands.

A short protocol for protein staining with Coomassie Brilliant Blue (CBB) G-250 in polyacrylamide gels is described without using organic solvents or acetic acid as in the classical staining procedures with CBB.

In classical protein staining protocols using Coomassie Brilliant Blue (CBB), solutions with high contents of toxic and flammable organic solvents ...

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the preparation of all-carbon quaternary centers. Though conjugate additions of organometallic reagents are typically performed utilizing highly reactive organolithium or Grignard reagents, organozinc reagents have garnered attention for their enhanced chemoselectivity and mild reactivity. Despite numerous recent advances with more reactive diorganozinc and mixed diorganozinc reagents, the generation of all-carbon quaternary centers via the conjugate addition of functionalized monoorganozinc reagents remains a challenge. This protocol details a convenient and mild &#8220;one-pot&#8221; preparation and copper mediated conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to afford a broad scope of all-carbon quaternary centers in generally excellent yield and diastereoselectivity. Key to the development of this technology is the utilization of DMA as a reaction solvent with TMSCl as a Lewis acid. Notable advantages to this methodology include the operational simplicity of the organozinc reagent preparation afforded by the utilization of DMA as a solvent, as well as an efficient conjugate addition mediated by various Cu(I) and Cu(II) salts. Moreover, an intermediate silyl enol ether can be isolated utilizing a modified workup procedure. The substrate scope is limited to cyclic unsaturated ketones, and the conjugate addition is impeded by stabilized (e.g., allyl, enolate, homoenolate) and sterically encumbered (e.g., neopentyl, o-aryl) monoorganozinc reagents. Conjugate additions to five- and seven-membered rings were effective, albeit in lower yields compared with six-membered ring substrates.

A simple and practical protocol for the efficient conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to furnish all-carbon quaternary centers was developed.

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the ...

Triazole and Tetrazole Functionalized Zr-MOFs Synthesis and Characterization

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. Given their coordinative nature, the organic ligands and strut framework can be readily removed from the MOF and/or exchanged with other coordinative molecules. By introducing target ligands to MOF-containing solutions, functionalized MOFs can be obtained with new chemical tags via a process called post-synthetic ligand exchange (PSE). PSE is a straightforward and practical approach that enables the preparation of a wide range of MOFs with new chemical tags via a solid-solution equilibrium process. Furthermore, PSE can be performed at room temperature, allowing the incorporation of thermally unstable ligands into MOFs. In this work, we demonstrate the practicality of PSE by using heterocyclic triazole- and tetrazole-containing ligands to functionalize a Zr-based MOF (UiO-66; UiO = University of Oslo). After digestion, the functionalized MOFs are characterized via various techniques, including powder X-ray diffraction and nuclear magnetic resonance spectroscopy.

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange 

Post-synthetic ligand exchange (PSE) is a versatile and powerful tool for installing functional groups into metal-organic frameworks (MOFs). Exposing MOFs to solutions containing triazole- and tetrazole-functionalized ligands can incorporate these heterocyclic moieties into Zr-MOFs through PSE processes.

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. ...