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Randall, S. George, P. Holland, B. Hedman, K. Hodgson, W. Tolman, and E. Solomon, J. Cramer and W. Tolman, Acc. Dai and T. Warren, Chem. Puiu and T. Warren, Organometallics 22, Vela, S. Stoian, C. M unck, and P. Smith, A. Sadique, T. Cundari, K. Rodgers, G. Lukat-Rodgers, R. Lachicotte, C. Flaschenriem, J. Vela, and P. Yu, J. Smith, C.
Flaschenriem, and P. Holland, Inorg. Cirera, J. Smith, R. Flaschenriem, S. Alvarez, and P. Diethyl ether and tetrahydrofuran THF were first sparged with nitrogen and then dried by passing through activated alumina columns. These reagents were used as received. Potassium hydride was obtained from Aldrich as a dispersion in mineral oil; using air-free techniques, it was filtered and washed with pentane to afford a dry powder. Using a Dean Stark trap, the mixture is refluxed with stirring for 4 h until no further water is collected.
Cooling the resulting solution gives a solid, the protonated b-diketimine as its tosylate salt, which is filtered and the solid is air-dried. The organic layer is separated and dried over MgSO 4. The volatiles are removed in vacuo to. The slurry is stored at 35 C overnight to encourage further crystallization. The product is isolated by filtration, washed with cold methanol, and dried to yield Properties The white microcrystalline solid forms colorless needles upon careful crystallization attempts.
It is soluble in common organic solvents. The b-diketimine HL Me,Me2 may be prepared analogously by substituting 2,6- dimethylaniline for 2,4,6-trimethylaniline in the above synthesis. Air-free procedures are required for use of potassium hydride, which can explosively generate hydrogen gas upon uncontrolled hydrolysis.
Hydrogen gas is generated in the procedure and should not be performed in a sealed flask. The reaction is stirred overnight and then filtered through Celite to remove excess KH to yield a bright yellow filtrate. The resulting dark green solution is filtered through Celite to yield a bright yellow filtrate. Removal of all volatiles in vacuo gives a dry yellow solid. Dissolving this solid in ca. Properties The compound is both light and air sensitive and is best stored in the dark.
Decomposition by light, air, or water results in black solutions or solids in which the free b-diketimine HL Me,Me3 may be detected by observation of its N-H 1 H NMR signal at d benzene-d 6. Thallium b-diketiminates exhibit low coordination numbers in the solid state. Budzelaar, N. Moonen, R. Smits, and A. Gal, Eur. Pangborn, M. Giardello, R.
Grubbs, R. Rosen, and F. Timmers, Organometallics 15, Hill, R. Pongtavornpinyo, and P. Hitchcock, Chem. Hill, P. Hitchcock, and R. Pongtavornpinyo, Dalton Trans. Cheng, P. Hitchcock, M. Lappert, and M. Zhou, Chem. Holland, T. Cundari, L. Perez, N. Eckert, and R. Lachicotte, J. Wiencko, E. Kogut, and T. Acta , Dias and J. Flores, Inorg. HOLLAND z The following procedure has been slightly modified from the literature by inclusion of a few more synthetic details as well as an increment in the scale for consistency of yield.
We have, however, encountered low yields and irreproducible results in syntheses that start from potassium diketiminate salts prepared in this way, presumably because of the variable quality of commercial KH. We describe here a reproducible and facile synthesis that uses benzylpotassium 3 as the potassium source, thus avoiding the use of potentially dubious KH and the hazards of explosion from the production of H 2 gas.
The THF-filled flask was taken into the glovebox and stored over metallic Na thin films. Anhydrous toluene and pentane were purchased from Aldrich in a sure-sealed reservoir 18 L and dried by passing through two columns of activated alumina and a Cu Q-5 column under N 2. Celite was dried under reduced pressure at C for 24 h.
C 6 D 6 was purchased from Cambridge Isotope Laboratories, degassed and dried over CaH 2, and then vacuum transferred to 4 A molecular sieves. Benzylpotassium was prepared by a procedure reported in the literature. In a two-neck mL round-bottomed flask, 1,4-pentanedione 6. To the mixture is added 7. After 6 h, a white precipitate begins to form, but the reaction must be continued for the full 3 days for complete conversion. The slurry is allowed to cool to room temperature and then filtered.
The filtered solid is dried under reduced pressure, and the filtrate is evaporated on a rotary evaporator. The dried mass is combined with the filtrate residue and the mixture is refluxed in ml hexane at 80 C for 1 h. After cooling the mixture, the slurry is filtered, and the solid residue is treated with ml of a saturated aqueous solution of Na 2 CO 3 and ml of CH 2 Cl 2.
The slurry is stirred until the solid dissolves, giving a yellowish organic solution and a pale yellow aqueous layer. The organic layer is separated. The solution is filtered again and dried under reduced pressure to yield a slightly yellow residue that upon washing with 50 ml of cold methanol 20 C yields white L Me,iPr2 Has a fluffy powder Properties L Me,iPr2 H is a white crystalline solid that is soluble in organic solvents including n-pentane and n-hexane.
It is recommended, however, to store the pure white free base under an inert atmosphere or under vacuum to avoid gradual tainting. Butyllithium is pyrophoric in air and should be handled exclusively under dry nitrogen or argon. This reaction is extremely exothermic, so the addition of n-buli should be performed at low temperatures and not be rushed. To the cooled solution a 1.
During the course of this time, a white precipitate gradually appears. The suspension is cooled to 35 C over 12 h, and the solid is collected by filtration, washed with 10 ml of cold hexane, and then dried under reduced pressure. After 12 h, a second batch of solid is collected via filtration, washed with cold hexane, and dried under reduced pressure. The combined yield for the two batches is 2. The salt has very low solubility in hydrocarbons such as n-pentane and n-hexane but can be dissolved in copious amounts of benzene and toluene.
The compound [L Me,iPr2 Li] x decomposes rapidly in halogenated solvents and upon exposure to air. It is recommended that solids not be stored for extended periods of time, even if inside a glovebox. For the preparation of its transition metal derivatives, it is preferable to use fresh [L Me,iPr2 Li] x or generate it in situ before use.
KCH 2 Ph is a highly pyrophoric that should be handled only in an inert atmosphere. Upon contact with O 2 or H 2 O, solid benzylpotassium will immediately deflagrate. This reaction to produce [L tbu,ipr2 K] x is extremely exothermic, so it is recommended that the addition of KCH 2 Ph be performed slowly and at low temperatures. A solution of L tbu,ipr2 H 2. To the thawing solution is added benzylpotassium 3 mg, 4. After stirring the solution at room temperature for 1.
The product is further washed with 15 ml of cold pentane, dried, and stored at 37 C. The degree of aggregation of this material was not investigated. The salt is insoluble in hydrocarbons such as n-pentane and n-hexane, and partially soluble in benzene, toluene, and Et 2 O.
It is also recommended that solids not be stored for extended periods of time, even if inside a glovebox. It is preferable to isolate fresh [L tbu,ipr2 K] x for subsequent use. Sloan Foundation fellowship to D. It is difficult to remove the final traces of toluene from the solid under vacuum, as is evident from 1 H NMR spectra. Jones, S. Liddle, C. Wilson, and P. Arnold, Organometallics 26, Bailey, R. Coxall, C. Dick, S. Fabre, L. Henderson, C.
Herber, S. Liddle, D. Lorono- Gonzalez, A. Parkin, and S. Parsons, Chem. Feldman, S. McLain, A. Parthasarathy, W. Marshall, J. Calabrese, and S. Arthur, Organometallics 16, Clegg, E. Cope, A. Edwards, and F. Mair, Inorg. El-Kaderi, M. Heeg, and C. Winter, Polyhedron 25, Studies on the vanadium chemistry of bulky b-diketiminates showed that this ligand did not coordinate to vanadium or titanium.
However, steric interactions between the tertbutyl groups and the neighboring 2,6-diisopropylphenyl groups push the latter toward the open side of the ligand and increase the extent to which the metal is blocked from additional ligands. Budzelaar sidestepped this problem using a convergent synthesis that couples the two sides of the ligand.
Half of this imine chloride is methylated to give a methyl tert-butyl imine, which is then deprotonated and treated with the remaining half of the imine chloride to give the final ligand. A method for preparing the lithium salt of this ligand is given here; please refer to the previous chapter to find a method for preparing the potassium salt of this ligand.
General Procedures All materials were purchased from Aldrich and used as received, unless otherwise specified. A solution of pivaloyl chloride 62 ml, 0. Although pivaloyl chloride is sensitive to water, predrying the triethylamine and dichloromethane is not required. The reaction is exothermic, so. The solution has a pale pink or green color, and a white precipitate is evident. After stirring the mixture for an additional 30 min, the slurry is chilled to 0 C, and the fluffy solid is collected by filtration.
Purity is determined by 1 H NMR spectroscopy. One hose attaches to a N 2 inlet, and the other is allowed to bubble through saturated sodium carbonate to neutralize gaseous HCl produced in the reaction. The headspace of the flask is purged with N 2 for 10 min, and the flow rate is reduced to a slow bubble.
Solid PCl 5 g, 0. Slow addition of PCl 5 is necessary because the reaction is exothermic. During the course of the reaction all solids dissolve, and the solution develops a yellowish color. The mixture is stirred for an additional 1 h after the addition of PCl 5 is complete. The two hose adapters are removed from the flask and replaced with ground glass stoppers. The third neck is fitted with a distillation head and benzene and POCl 3 are removed by distillation directly from the reaction flask at ambient pressure under a N 2 atmosphere.
Purity is established by 1 HNMR spectroscopy. Methyllithium is pyrophoric in air and should be handled exclusively under dry nitrogen or argon. This reaction is extremely exothermic, so the addition should be performed carefully at low temperatures. It is easier to perform the reaction in a cold well in a drybox, if the equipment is available.
The mixture is allowed to slowly warm and stirred at ambient temperature, upon which a white precipitate is observed. Caution: A slow flow of N 2 through the septum and out to an oil bubbler is necessary to ensure that the reaction vessel does not develop pressure since the reaction is exothermic and the ether solvent is quite volatile.
After 12 h, the mixture is exposed to air by removing the septum and ice about 5 g is carefully added in small portions until effervescence ceases. Water ml is added, and the mixture is transferred to a separatory funnel where the aqueous layer is removed. The organic layer is extracted twice more with The checkers distilled at C at 7 mbar.
The checkers report that a 3-h reaction time is sufficient for full conversion. The volatile materials are removed under vacuum to afford a light yellow oil. The oil is stable for months to air and moisture. Purity is established by 1 H NMR spectroscopy. The solution is chilled to 78 C and n-butyllithium 76 ml, 2. The flask is sealed with a ground glass stopper and the stopcock is left open to allow butane to escape. The mixture is allowed to slowly warm to ambient temperature for 16 h.
The resulting slurry is allowed to slowly warm and stirred at ambient temperature for 18 h, whereupon the The checkers conducted the reaction at 0 C and did not distill the product. The crude product was assayed by 1 H NMR spectrum and was used in subsequent steps without further purification. The mixture is removedfromthegloveboxandheatedatrefluxinanoilbathfor2hundern 2. The slurry is cooled and exposed to air where it is carefully quenched with ice and water ml.
The mixture is transferred to a separatory funnel, and the aqueous layer is discarded. The organic layer is extracted twice more with water 2 ml , dried with anhydrous MgSO 4, and filtered through coarse filter paper. The volatile materials are removed under vacuum to afford a sticky yellow solid.
This solid is dissolved in ml of boiling hexanes, and the extract is slowly cooled to 25 C to give colorless block-shaped crystals of L tbu,ipr H in two crops When stored in air, L tbu,ipr H slowly turns yellow over a period of weeks; therefore, keeping L tbu,ipr H under an atmosphere of N 2 is appropriate for longterm storage. The 1 H NMR spectrum of L tbu,ipr H shows overlapped and broadened peaks due to the mixture of bis imine and imine enamine tautomers.
At 70 C in CDCl 3, the spectrum is better resolved. The major component ca. The minor ca. The remaining alkyl and aryl resonances from the imine enamine tautomer overlap with the major component. This reaction is extremely exothermic, so n-buli should be added slowly.
It is important to vent the reaction. This manipulation is also possible outside of the glovebox by adding n-butyllithium through a septum and allowing butane to escape through an oil bubbler. The flask is kept open while a solution of n-butyllithium Following addition of butyllithium, the mouth of the flask is sealed with a ground glass stopper and the stopcock is left open to allow additional butane to vent.
After stirring the solution for 30 min, the flask is closed, removed from the glovebox, and the solution is heated in a 60 C oil bath for 3 h. The volatile materials are removed in vacuum, leaving a yellow residue. The flask is returned to the glovebox. The solid is freed from any excess butyllithium by briefly shaking with pentane ml and decanting the supernatant. This wash is repeated with an additional portion of pentane ml , and the yellow solid is dried under vacuum to give L tbu,ipr2 Li THF Additional product is obtained by reducing the volume of the combined pentane washes to 30 ml and cooling to 45 C.
This solid is collected on an oven-dried fritted glass funnel and washed with cold pentane 10 ml, 45 C to obtain additional L tbu,ipr2 Li THF 2. It is suitable for most further syntheses, but recrystallization is recommended to ensure complete removal of traces of butyllithium before use with metal salts that are prone to reduction, for example, copper i derivatives. Bailey, L. Watson, J. Mindiola, Organometallics 24, Basuli, R. Clark, B. Holland, Chem. Eckert, E. Bones, R. Eckert, J. Vaddadi, T.
Cundari, J. Smith, E. Gregory, R. Holland, Organometallics 24, Spencer, N. Aboelella, A. Reynolds, P. Holland, and W. ScCl 3 THF 3 is prepared by a modified literature procedure. It should be noted that the checkers did not use a swivel frit, but rather, conducted manipulations inside a glovebox using a commercially available microporous frit medium porosity.
The reaction mixture is heated at reflux for 3 h during which period the mixture changes from a cloudy white suspension to a clear yellow solution. The solvent is removed by rotary evaporation to give ScCl 3 H 2 O 6 as a thick yellow oil. Precipitation of a white solid, followed by a gradual change to a clear yellow solution, also occurs during this period. The reaction mixture is then heated at 86 C for 18 h, and the solvent is removed by rotary evaporation to afford an oily yellow solid.
The moisture-sensitive mixture is quickly attached to a swivel-frit 1 apparatus and evacuated. Et 2 O ml is added to the residue, which is then stirred for 20 min and filtered. The fine white powder is washed with Et 2 O 4 50 ml and the solvent is removed in vacuo.
Properties The product is a fine white powder that must be stored under an inert atmosphere as it rapidly absorbs moisture from air. Toluene 90 ml is vacuum distilled into the evacuated flask at 78 C, and the mixture is heated with stirring at reflux for 16 h. During this period, the solution gradually changes from almost colorless to pale yellow.
The residue is sonicated for 10 min in hexanes 60 ml , followed by cold 78 C filtration. Similar yields were obtained. Properties Complex L Me,iPr2 ScCl 2 THF is an off-white solid that is soluble in most organic solvents, such as diethyl ether, THF, hexanes slightly , toluene, and bromobenzene; however, prolonged exposure to chlorinated solvents such as dichloromethane or chloroform results in decomposition.
Although L Me,iPr2 ScCl 2 THF rapidly decomposes upon exposure to even trace air or moisture, samples can be stored indefinitely under an inert atmosphere. Toluene ml is condensed into the vessel, which is then sealed and heated at C for 3 days. It is necessary that the mixture be constantly stirred. Quiescent mixtures generally require an additional 3 4 days. During this time, the color changes from pale to deep yellow.
Such colors are generally supplanted by the usual deep yellow as time progresses. If dark colors are observed during or persist throughout the reaction, the normal workup protocol outlined abovewill still give the desired product, albeit in somewhat lower yields. Scandium Trichloride Tris Tetrahydrofuran and b-diketiminate 23 Figure 1. Heavy-walled reactor used in this procedure.
The bright yellow residue is sonicated for 10 min in hexanes ml and cooled to 78 C, and the slurry is filtered. Properties Complex L tbu,ipr2 ScCl 2 is a pale yellow solid that is soluble in most organic solvents, such as diethyl ether, THF, hexanes slightly , toluene, and bromobenzene. For a description of the equipment and techniques used in conducting this chemistry, see: B. Burger and J. Waydaand M. Darensbourg, eds. Manzer, Inorg. Piers, L.
Lee, L. Knight, M. Parvez, M. Elsegood, and W. Clegg, Organometallics 20, Piers, and M. Parvez, J. The THF-filled flask was transferred into the glovebox and stored over metallic Na thin films. Anhydrous toluene and pentane were purchased from Aldrich in a sure-sealed reservoir 18 L and dried by passing through two columns of activated alumina and a Cu Q-5 column under a pressure of N 2.
The vessel is sealed inside the glovebox with a Teflon pin. After the mixing, the slurry becomes a green colored solution. The reaction mixture is transferred out of the glovebox and heated to reflux 80 C for 12 h, during which time the solution color turns to deep green. After this time, the solution is brought into the glovebox, transferred to a mL filter flask, and evaporated under reduced pressure.
The green mass is extracted with ml toluene, and the extract is filtered through Celite, which is then washed with toluene several times until the washed solution is nearly clear. The green filtrate is then reduced in volume until solid begins to form on the sides of the flask. To expedite drying of the materials, the crystals and solids are washed with 25 ml pentane and then dried under vacuum. The combined yield is 6.
UV vis toluene e in M 1 cm 1 : , nm. Both the solvent-free and THF complexes have similar solubilities, being soluble in toluene, benzene, and THF, and insoluble in pentane and hexane. The complex is partially soluble in Et 2 O. The complex gradually decomposes in CH 2 Cl 2. Decomposition to unidentified products also occurs when either complex is exposed to air, moisture, or halogenated solvents such as CCl 4. When combined with B C 6 F 5 3, the complex forms a highly active catalyst for the polymerization of propene and 1-hexene.
Likewise, THF can be readily displaced when the alkyl substituent is sterically encumbering. In a conical flask, [L tbu,ipr2 Li] x 1. During the addition of the salt, the blue color of the TiCl 3 THF 3 suspension gradually changes to greenish brown. Upon completing the addition, the thick-walled reaction vessel Fig. The reaction vessel is brought outside the glovebox and heated at C for 3 days with vigorous stirring.
Within 2 h of initial heating, the color of the solution changes to intense green. After completion of the reaction, the reaction vessel is brought back into the glovebox, the solution is filtered through a Celite bed, and the volume of the filtrate is reduced to 20 ml until green microcrystals begin to form.
After allowing the solution to warm up to the box temperature to redissolve the crystals, 25 ml of hexane is added and the solution is cooled to 35 C for 24 h. At this time, intense green microcrystals of L tbu,ipr2 TiCl 2 are separated after filtering the solution through a medium porosity frit, and the solids are washed with 10 ml of hexane to afford 1.
To obtain reproducible recrystallization results, it is highly recommended to have a homogeneous solution prior to cooling. Properties Complex L tbu,ipr2 TiCl 2 intense green is indefinitely stable at 35 C and in the absence of oxidants or protic media. Inside the glovebox, both solutions are loaded in a or mL heavy wall glass round-bottomed pressure vessel Fig. After mixing, the color of the solution gradually changes to red-brown.
The mixture is transferred out of the glovebox and refluxed with stirring at 90 C for 30 min, upon which the solution rapidly turns to deep brown-red. The solution is cooled to room temperature, and then the flask is brought into the glovebox and transferred to a Schlenk flask. The volatiles are removed under reduced pressure inside the glovebox to yield a red-brown solid. The flask is sealed with a glass.
The flask is then heated at C for 45 min under dynamic vacuum on a Schlenk line. The flask is transferred into the glovebox, and the deep green mass is washed with 25 ml of hexane and then extracted with ml of toluene.
The toluene solution is filtered through a bed of Celite, rinsing the residue with 10 ml portions of toluene until the filtrate is almost colorless approximately three portions. The volume of the deep green filtrate is reduced to 50 ml until a solid begins forming on the sides of the flask. The solution is capped with a rubber stopper and cooled to 35 C for 2 days to obtain bright green crystals of L Me,iPr2 VCl 2.
After filtration, the green crystals are collected and dried under reduced pressure. The filtrate is then concentrated 25 ml and stored at 35 C for 1 day to afford a second batch of product, which is dried under vacuum.
The combined yield is 3. UV vis toluene e in M 1 cm 1 : , , , nm. IR Nujol, KBr plates m , s , s , m , w cm 1. Complex L Me,iPr2 V Me 2 is not as active catalyst as the titanium analogue for the polymerization of propene and 1-hexene when activated with B C 6 F 5 3. Sur, J. Evans, J. Soc Basuli, D. Adhikari, J. Bailey, F. Kilgore, X. Hu, K. Meyer, M. Pink, J. Mindiola, Angew. C 6 D 6 was predried with sodium and stored under vacuum over 4 A molecular sieves.
Molar magnetic susceptibilities were corrected for diamagnetism using Pascal constants. Butyllithium was purchased as a 1. VCl 3 anhydrous and CrCl 3 anhydrous were purchased from Strem. The solution is cooled to 30 C and then treated with ml The mixture is allowed to warm to room temperature and the yellow solution thus obtained is added to a mL flask containing a red slurry of g The resulting dark red-brown solution is stirred overnight at room temperature giving a dark green solution.
The solution is evaporated to dryness; the residue is triturated three times with 20 ml of diethyl ether to give a green solid, discarding the ether. The residue is then extracted three times with toluene totaling ca. The resultant solution is concentrated to approximately one-third of its original volume and left to crystallize at 30 C to afford red-brown crystals.
Found: C, UV vis toluene : l max e in M 1 cm 1 , , nm As outlined in the entry for L Me,iPr2 VCl 2 described herein , b-diketiminato vanadium dihalide complexes have been explored as precatalysts for a-olefin polymerization and may be alkylated to give dialkyls LVR 2. The color of the solution changes from purple to red-brown. After stirring the solution at room temperature overnight, the THF is removed and the solid is extracted with three mL portions of toluene.
The solution is then filtered through Celite, rinsing with ca. The toluene is then removed in vacuo and the solid is dissolved in ca. The resulting THF solution is concentrated to 20 ml in vacuo and allowed to crystallize overnight at 30 C. A dark red microcrystalline powder is isolated by filtration. After washing with ca. The solution is red-brown in THF, toluene, and benzene, but changes to a yellow color in ether.
Related Compounds b-diketiminato chromium halide and alkyl complexes have been explored as precatalysts for alkene polymerization. Herwig and H. Zeiss, J. Kim, M. Fevola, L. Liable-Sands, A. Rheingold, and K. Theopold, Organometallics 17, Gibson, C.
Newton, C. Redshaw, G. Solan, A. White, and D. Williams, Eur. MacAdams, W. Kim, L. Liable-Sands, I. Guzei, A. Theopold, Organometallics 21, MacAdams, G. Buffone, C. Incarvito, A. Theopold, J. Buffone, D. Incarvito, H. Golen, A. Theopold, Chem. Monillas, G. Yap, L. MacAdams, and K. Tsai, P. Wang, S. Chen, and J. Chen, J. General Procedures All reactions were performed using standard Schlenk and drybox techniques. All the solvents except dichloromethane P 4 O 10 were distilled from sodium under dry nitrogen.
Step 1: A suspension of KH 0. After filtration, the light yellow filtrate is concentrated to ca. Yield: 1. The mixture is allowed to warm to room temperature and stirred for 14 h. The precipitate is removed by filtration. The yellow filtrate is concentrated to ca. The bound THF ligand may be readily removed by refluxing in toluene see below and may be displaced by other Lewis bases such as a N-heterocyclic carbene ligand.
All volatiles are removed in vacuo and bright yellow microcrystals are obtained. Properties and Related Compounds The product is soluble in toluene and insoluble in Et 2 O and pentane. Upon completion of the addition, the solution is allowed to warm to room temperature and stirred for 12 h.
The solution is concentrated to approximately 20 ml under reduced pressure until the product precipitates, which redissolves with mild heating. Cooling for 24 h at ca. The mixture is allowed to warm to room temperature and then stirred for additional 3 h and then filtered. The solution is concentrated to 10 ml and cooled overnight at 35 C to yield colorless crystals.
The Et 2 O coordinated to Li is somewhat labile. This b-diketiminate has been reported to be isolated as the three-coordinate complex L Me,iPr2 ZnCl via careful crystallization. Three-coordinate alkyl complexes L Me,iPr2 Zn-R may be formed by alkylation with alkyllithium reagents.
Monoethyl complexes may also be prepared byuseofznet 2 withthefreeligandhl. Chai, H. Zhu, K. Most, H. Roesky, D. Vidovic, H. Schmidt, and M. Noltemeyer, Eur. Zhu, H. Roesky, C. He, H. Noltemeyer, Organometallics 23, Roesky, and J. Magull, Organometallics 23, Roesky, Z. Yang, V. Jancik, R. Herbst-Irmer, H. Zhu, A. St uckl, H. Roesky, J. Magull, A. Bencini, A. Caneschi, and D.
Gatteschi, J. Sorace, C. Golze, D. Gatteschi, A. Bencini, H. Chai, and A. St uckl, Inorg. Power, J. Ding, H. Roesky, M. Noltemeyer, H. Schmidt, and P. Power, Organometallics 20, Prust, A. Stasch, W. Zheng, H. Roesky, E. Alexopoulos, I. Schuchardt, Organometallics 20, Prust, H. Hohmeister, A. Stasch, H. Magull, E. Hao, C. Roesky, G. Bai, H. Noltemeyer, Chem. Varonka and T. Coates, Angew. Dove, V. Gibson, E. Marshall, A. Williams, Dalton Trans. Wang, B. Quillian, P.
Wei, H. Wang, X. Yang, Y. Xie, R. King, P. Schleyer, H. SchaefferIII, and G. Robinson, J. Reaction flask used in this procedure. Glassware was dried at C overnight. Pentane and toluene were purified by passing through activated alumina and Q-5 columns from Glass Contour Co. Before use, an aliquot of each solvent was tested with a drop of sodium benzophenone ketyl in THF solution. Celite was dried overnight at C under vacuum. Toluene 40 ml is added to dissolve the solid, forming a pale yellow solution, and while stirring at 25 C, solid FeCl 2 THF 1.
The flask is then sealed and moved from the glovebox to the Schlenk line where it is heated in an oil bath, gradually raisedfrom25to C. After18 h,thered-orangesuspensionisallowedtocooland is evaporated to dryness. The flask is then returned to the glovebox, and the solids are washed with pentane 3 10 ml to remove unreacted LiL Me,iPr. The etherate complexes can be desolvated, regenerating [L Me,iPr FeCl] 2 2LiCl, by dissolving the yellow solids in toluene and heating at C for 12 h and evacuating to dryness.
The by-product LiCl can be removed by Soxhlet extraction. The insoluble orange powder obtained above is slurried in pentane 3 20 ml and collected by gravity filtration in a glass thimble consisting of a coarse glass frit with a 0. The thimble containing the washed orange solid is then placed in the Soxhlet extractor fitted with a mL round-bottomed flask containing a large magnetic stir bar and toluene ml on the lower end and a condenser with a resealable Teflon valve. Note: It is beneficial to measure the antechamber and assembled Soxhlet extraction apparatus prior to loading in the glovebox, because the assembled apparatus may be quite long.
If the assembled apparatus is too long, the condenser can be attached to the flask outside the box with a vigorous flow of N 2. Under a N 2 atmosphere on the Schlenk line, the apparatus is heated in a C oil bath.
After 24 h, the red suspension is evacuated to dryness, leaving a solid orange residue. It reacts slowly with CH 2 Cl 2. Additional characterization in noncoordinating solvents is limited by low solubility. It is sensitive to air and moisture. Related Compounds This compound is a precursor to a wide variety of three- and four-coordinate iron ii complexes, including alkyl, aryl, hydride, sulfido, amido, and fluoride.
Reduction to an iron i dinitrogen complex provides a pathway to iron i alkyne, alkene, carbonyl, isocyanide, arene, and phosphine complexes, as well as a reactive iron iii imido complex. Sloan Foundation Research Fellowship. Kern, J. Winter, Inorg. Holland, Acc.
Sciarone, A. Meetsma, B. Hessen, and J. Teuben, Chem. The charged flask is removed from the glovebox, and the reaction mixture is heated in an oil bath at C for 18 h during which time it turns very dark red in color. In the first month of its existence alone, no fewer than newspaper articles were. Nine errors in credit report I HAVE been following with interest recent reports about spiralling credit-card debt and the measures the authorities are putting m place to ensure the problem does not get out of hand.
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Park MRT station at about 3. The bus driver not only smiled but also wished every passenger who boarded the bus Happy New Year! I was surprised as this was. Many thanks. Pay more? Based on the current economic. Courting disaster at intersections THERE has been a high incidence of road accidents m the first week of the year.
Moat of these occurred at intersections and some resulted m pedestrian fatalities. At first, I was bewildered to learn that Singapore Press Holdings SPH was increasing its newspaper prices by up to 10 cents tor subscribers. However, it should conduct on-site inspections to evaluate if motorists deserve such a scheme. Most of the junctions with the Left Turn on Red scheme are potential accident areas.
Madam Ng said her sister decided not to press charges against her foreign maid for theft because it would have meant that she would be unable. Stocks going fast! The Straits Times home Saturday, January 17, She does things that I would not even do myself. Mrs Josephine Fong, 33, an accountant who has sent her 1 0-mon th-ol d daughter to a nanny for the past nine months. Now warning 2 CJ sets mid-Feb deadline K.
If this were so, we urge SPH to provide more incentives rather than relying solely. Shrek hongbao up for grabs MAKE your hongbao stand out this Chinese New Year give out speciallydesigned ones featuring that green ogre Shrek and his friends. Air Asia chief Tony Fernandes let slip the news yesterday while He said that no.
Filipino Manuel Gamboa, 32, an interior designer who has been living and working here for the last seven years,. Man jailed tor sex offences against 3 young relatives High Court worker jailed for three years and nine months for unnatural acts against male kids aged 11 r 12 and 17 A HIGH Court employee was yesterday sentenced to three years and nine months m jail for committing various unnatural.
His niece is schizophrenic and mildly. Four nabbed for bid to sell fake pills FOUR women, all Chinese nationals, have been arrested for trying to sell fake Cialis pills here. Cialis, which contains tadalafil, is used to treat male erectile dysfunction. The yellow pills are distributed locally only by Eh Lily and its agents. Health Sciences. Once told that. The Land Transport Authority said the tender will open next Monday at 9am instead of the usual noon and it will close the.
He is also a strong supporter. Discussing race relations with them over mcc. Why cant we he kawan-kawan As four men tuck into an order ofmee goreng, mosque leader Suratman Hussein puts calligraphy teacher Tan Tiow Siong at ease by saying m Hokkien: Jiakjiak kao poem. Maijiak si poon Eat yourfiU. The group took part m the. You go out fishing all night and battle the elements You return with a good.
The skeleton of the adult male lion was found at Saqqara, in what was originally the tomb. The find by researchers from the university confounds the. But what makes the twostorey home different from any. I J-aaJB. Registration Fee Which means. The Straits Times asia Saturday, January 17, More evidence linking Sars to civet cats W. Kong but was later cleared of the disuse, bis died of pneumonia, officials saW yesterdiy.
TIN yeir-oW. The men, m detention centres m Guangdong, Hainan, Fujian and Anhui provinces, delivered a. Japan has protested against the plan to issue the stamps. New tactics in Karachi car bombing worry police KARACHI Police tightened security around Pakistani churches and mosques yesterday following the explosion of a powerful car bomb outside a Christian reading room that caused heavy damage ana injured 15 people.
A survey of street children is under way after Prime Minister Thaksin Shinawatra met five street children who told him about their plight. Fon, whose eight-year-old sister was raped. What is palatable and refreshing. However, Malaysia is m creasingly being seen as a.
Wolves boss Dave Jones, on the answer he gets from Manchester United manager Alex Ferguson each time he asks if the English soccer champions have players to loan. The year-old Manchester United midfielder has. Udinese v Parma Live. Tomorrow Ancona v Perugia. Bologna v Chievo, Brescia v Milan Live. Ch2l Monday. Ch2l 11pm , Reqqina v lecce, Roma v Sampdoria Live. Valladolid v Valencia Live. Ch2i, tomorrow. Barcelona v A. Bilbao Live, Channel i. Ch22, H. Mailorca v R. Madrid v.
Valencia face up to Valladolid threat MADRID Valencia may not have very long to enjoy their role as league leaders because the Spanish fixtures computer has decreed that today, they must travel to Valladolid their bogey team m recent years. But a joke by Wolverhampton boss Dave Jones this week about his efforts to sign new players provided the perfect illustration of the gulf between top and bottom m the Premiership.
Jones, whose. He cannot. Rewards for golden 30 G. The chief coach. Wie outdrives men to cheers GOLF yard tee shots and three birdies earn praise but she needs better score to make the cut HONOLULU Michelle Wie hammered two yard drives, made three birdies and left a handful of men embarrassed and the rest awed along the way.
Making her PGA. PMi 3. We look at your face and see a friend In sweet slumber though In our hearts we know you have left us forever. The playful smile, silly Jokes, funny faces, songs you hummed and the adventures we. The Family Of The Late NG SONG KOK Departed 10 January wish to express their heartfelt thanks and appreciation to relatives, friends, colleagues and business associates for their kind assistance, attendance, condolences, donations and wreaths during their recent bereavement.
Special thanks also to the Management and colleagues of Atwln. US industrial output growth slows; consumers more upbeat Production at US factories, mines and utilities rose only 0. Mr Templeton, 45, was named to the board. But the embattled firm declined to say how the problems would affect its bottom. Increased exports of electronics components and nonelectronics goods such as pharmaceuticals and petrochemicals drove December exports up.
Dr Balakrishnan THE Government has launched an online licensing service which aims to cut the red tape and take the hassle out of applying for. Barely four years after setting up Midas Holdings to tap business opportunities m. In Shanxi: Midas designs, manufactures and installs polyethylene pipes for use m various types of gi and water piping networks.
In Jilin: The company specialises m making aluminium alloy extrusion pnxlucts mainly for the transportation industry. Over at CX Tang, minority shareholders who are m. Dealers said trading was muted. Simon Cheong sells Get rewarded flk. Disney Enterprises, Inc. J Tee off on our specially designed. National Service Resort CC. ORA Youth v Police 6pm. Nomads v CSC B 7.
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Can anyone help? I have been looking for textbook everywhere, with no luck. Also, have been looking for last dance. No luck. I have the 9th edition, but need the 10th. If anyone finds please let me know. Anyway thanks a lot! Thank you kind sir, you helped me finding a book I was looking for since 2 weeks. My respect to you! I know its out there somewhere since he told us that the book is on a torrent site if we look hard enough for it.
Please notify me of the site offering this book for free download. Thank you, D. Laurence Rogers. Have you considered that trying to acquire a book for free is exactly the same as shoplifting. If you do it you ARE a criminal. Shoplifters go to jail. They write at night, early in the morning, any moment they can snatch while holding down sometimes up to 2 jobs to make ends meet. Stealing online is no different than someone breaking into your home and stealing your stuff. Would that be ok with you?
Do you work for free? Would you work for free? Authors put many long hours, sometimes years into writing a book. They go through many rejections before a publisher accepts it. If they self-publish they spend hard earned money trying to promote the book. Respect that. Pay for the book. Screwing over students, making one small revision so they can resell the new edition for full price. Screw the publishers, I pirate with pride. Why such blind allegiance to the law?
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Brownson, and Mark V. Wegner, , American Public Health Association. I have tried so many sites, it may be that the book it too new but hopefully someone finds it. Many thanks for this, much appreciated. Thanks again. Copying data is not stealing, as the owner of the original data gets to keep it. Sharing is caring. There are still ways to provide something back to a community, by uploading and sharing more rather than selfishly leeching and hoarding.
Long live the freedom of information and the ability to share ones and zeros how we please. Sensation and Perception, 4th edition. Sinauer Associates. Thanks Much! If I had labored instead, could have enough money to by them! I have searched and searched.
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All the editions of the books I find are 1 or 2 editions behind. Thanks for the info nevertheless. Hi can anyone please help me find this book. Thank you. Can somebody help me please, been looking for a book to no avail, Elementary Principles of Chemical Processes, 4th Edition solution manual. If anyone can help me with this i will be forever grateful. Anyone send me a link to download information systems analysis and design by shouhong wang and hai wang ebook.
I would really appreciate your help. Help me find this plz I have looked everywhere, but the book is pretty new. Comprehending the proper question to ask is generally way more important than having a prepared response. First-class questions dispute your own reasoning. Research studies are quite clear that we value people that take note of us.
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Schermerhorn Jr. Can anyone please help me find the solutions manual for Signals and Systems: a matlab approach by Oktay Alkin? I need fundamental accounting principles 16th Canadian edition,McGrraw-Hill ryerson limited, Oh fine : I will share this immediately worldwide, with the authors, suffering daily from the thefts! Hi anyone has a copy of Technical Communication seventh edition? Skeptical about torrenting books or anything. All about that learning so I appreciate the work you do :.
Sher, Richard B. Can anyone find it? But can not find it anywhere. Please Help. Pls help I searched everywhere but no result. It was released in and only available as paperback until the time I typed this, no epub or pdf. I cant spend 70 bucks on a singular book T-T. Author not required. Email not required. Reply Wickedassofo halleluja Jan 22, am Dude. Reply Anonymous May 23, am A really good site for any book is gen.
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