求助这个反应？ 有钠的，有钾的，钠钾就不知道了 submitted by henry strong,* paul j. krusic,t and joseph san filippo, jr.* checked by scott keenans and richard g. finkes carbonylferrates have been the subject of many studies. the well-defined mono-, di-, and trinuclear species [fe(co),]'-, [fe2(c0),,l2-, and [fe,(c0)ll]2- have been obtained by a variety of methods'-, in varying yields and degrees of convenience. the procedures described here provide uniform, convenient, high-purity, high-yield syntheses of the sodium salts of these three important reagents. in addition, the preparation of the bis bnitrido- bis(triphenylphosphorus)(l + )] salt of [fe,(co), j2 - by metathesis of [(ph,p),n]cl with na2[fe,(co), 1] is presented.bony1 (14.04 g, 72.0 mmol) in tetrahydrofuran (200 ml) is added over a 30- min period with stirring to the previously described solution of (naphthalene) sodium. following a work-up procedure equivalent to that described above, the orange precipitate that is obtained is rinsed with three 200-ml portions of pentane. on drying under vacuum the orange solid yields 13.6 g (99%* based on iron pentacarbonyl) of bright yellow na,[fe,(co)j. the addition and removal of thf causes a reversible color change.2b elapsed time for the total synthesis is -3 h. caution. dry na,[fe2(co),] is a pyrophoric substance. disodium undecacarbonyltriferat~2- ), na2[fe,(co), 1], is prepared by a modification of the above procedure. thus, in a nitrogen flushed dry box, a 250-ml, single-necked, round-bottomed flask equipped with a teflon-coatkd stimng bar is charged with 1.84g (44 mmol) of sodium dispersion and capped with a rubber septum stopper. the flask is removed from the dry box and cooled in an ice bath; a solution of naphthalene (6.00 g, 47.0 mmol) in tetrahydrofuran (150 ml) is introduced by cannula, and the resulting mixture is stirred for 2 h. a modified (see above) 1-l three-necked flask equipped with addition funnel and teflon-coated stirrer bar is charged with 10.07 g (20.0 mmol) of fe,(co),,, capped with a rubber septum, and flushed with nitrogen before adding thf (125 ml). the flask is placed in a dry ice-acetone bath, and the solution of sodium naphthalene is transferred through a cannula into the 200- ml addition funnel. this solution is added slowly over a period of 1 h to the chilled, well-stirred solution of fe,(co),, in thf. this order of addition is essential; reversal of the indicated order leads to substantial contamination of the product by unidentified side products. the resulting mixture is stirred for an additional 2 h before it is permitted to warm to ambient temperature. the flask is then transferred to the dry box, and the contents are concentrated under vacuum to dryness. the remaining dark red-brown solid is rinsed with three 200-ml portions of pentane and dried under vacuum once again. the isolated yield of na2[fe,(co),,] is 10.2g [98%t based on fe,(c0)12]. approximate elapsed time for total synthesis is 4 h. caution. dry na,[fe,(co), ,] is a pyrophoric substance. bis~-nitrido-bis(triphenylphosphorus~+l )] undecacarbonyltriferrate(2 - ) is obtained by treating a solution of na2[fe3(co)i 1] (1.2 g, 2.3 mmol) in 25 ml of anhydrous methanol, which is distilled from mg(och,), and is contained in a 250-ml, single-necked, round-bottomed flask with a solution of [(ph,p),n-jc16 (aldrich) (3.0 g, 5.2 mmol) in methanol (25 ml.) the dark red-brown solid that precipitates is collected by suction filtration on a *checkers obtained a yield of 88% after having initial dficulties in dissolving sodium. ?checkers obtained 57% yield. 206 metal carbonyl anion complexes medium-porosity frit under an inert atmosphere. recrystallization from dichloromethane as previously described3 yields 2.9 g (81%)* of crystalline, dark red-brown crystals of [(ph,p),n],[fe,(co), ,i. roperties disodium tetracarbonylferrate(2 - ) is a snow-white solid that is extremely sensitive to oxygen. it has a reported' solubility of 7 x m in thf and can be stored for moderate periods of time in an inert atmosphere, at room temperature, if kept in the dark. the ir spectrum, recorded in n,ndimethylformamide (dmf), exhibits a stretching frequency at 1730 an-', consistent with previous literature report^.^ the structure of the [fe(co),]'- anion has been established by x-ray,' and the utility of this reagent has been discus~ed.~ disodium octacarbonyldiferrate(2 - ) has been reported previously.'b this extremely air-sensitive solid is largely insoluble in most organic solvents, with only marginal solubility in thf. its ir spectrum, recorded in dmf, shows the following co stretching vibrations: 1835 (w), 1860(s), and 1910 (m) cm- consistent with previously reported valueszb a single-crystal x-ray structure determination of the [fez(c0),]' - anion has been carried out." disodium undecacarbonyltriferrate(2 - ) is a well-known substance that has also been characterized structurally.' ' the ir spectrum of this material, recorded in dmf, shows co stretching bands at 1940(s), 1915 (m), and 1880 (w) cm- ', consistent with values observed previ~usly.~*'' 查看更多
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