Potassium organometallics

Both sodium and potassium salts are natural constituents of body tissues and fluids as Na+ and K+ ions, respectively, and are not themselves toxic at normal physiological levels. The oxides and hydroxides of both these metals are very caustic, corrosive substances that damage exposed tissue. Oxides are formed by the combustion of sodium and potassium organometallics, and hydroxides are produced by the reaction of the oxides with water or by direct reaction of the organometallics with water, as shown below for cyclopentadienylsodium ... 

Table 10. Fluorination of Sodium and Potassium Organometallic Derivatives...

Allylic potassium organometallics derived from BuLi-r-BuOK react with electrophiles predominantly at the a-position. °... 

Besides [Ni(CO)4] and organometallic compounds discussed in the next section, nickel is found in the formally zero oxidation state with ligands such as CN and phosphines. Reduction of K2[Ni (CN)4] with potassium in liquid ammonia precipitates yellow K4[Ni (CN)4], which is sensitive to aerial oxidation. Being... 

In general, the reaction can be performed only with organometallics of active metals such as lithium, sodium, and potassium, but Grignard reagents abstract protons from a sufficiently acidic C—H bond, as in R—C=C—H —> R—C=C—MgX. This method is best for the preparation of alkynyl Grignard reagents. ... 

Other organometallic compounds that are hydrolyzed by water are those of sodium, potassium, lithium, zinc, and so on, the ones high in the electromotive series. Enantioselective protonation of lithium enolates and cyclopropyllithium compounds have been reported. When the metal is less active, stronger acids are required. For example, R2Zn compounds react explosively with water, R2Cd slowly, and R2Hg not at all, though the latter can be cleaved with concentrated HCl. How-... 

Many organometallic compounds are best prepared by this reaction, which involves replacement of a metal in an organometallic compound by another metal. The compound RM can be successfully prepared only when M is above M in the electromotive series, unless some other way is found to shift the equilibrium. That is, RM is usually an unreactive compound and M is a metal more active than M. Most often, RM is R2Hg, since mercury alkyls are easy to prepare and mercury is far down in the electromotive series." Alkyls of Li, Na, K, Be, Mg, Al, Ga, Zn, Cd, Te, Sn, and so on have been prepared this way. An important advantage of this method over 12-36 is that it ensures that the organometallic compound will be prepared free of any possible halide. This method can be used for the isolation of solid sodium and potassium alkyls." If the metals lie too close together in the series, it may not be... 

Eerrocene (1) was the first sandwich complex to be discovered, thereby opening a wide and competitive field of organometallic chemistry. The formation of ferrocene was found at almost the same time in two independent studies on July 11, 1951, Miller, Tebboth, and Tremaine reported that on the passage of N2 and cyclopenta-diene over a freshly prepared mixture of reduced Ee (90%), alumina (8%), potassium oxide (1%), and molybdenum oxide (1%) at 300°C, yellow crystals identified as Cp2Ee (Eig. 1) were obtained [1]. Due to the low yields obtained (3 g starting from 650 g ferric nitrate), doubts remain as to whether Ee(0) was the... 

See related haloalkenes See other organometallics 3471. Potassium tricarbonyltris(propynyl)molybdate(3—)... 

Alkali metals, particularly potassium 2. Alkali metal alkoxides and amides 3. Organometallics ... 

Ethyl pyridine-2-acetate and ethyl 6-methylpyridine-2-acetate have previously been prepared by carboxylation of the lithio derivatives of a-picoline and lutidine, respectively. Use of ethyl carbonate to acylate the organometallic derivative avoids the intermediacy of the (unstable) carboxylic acid, and the yields are better. In the present procedure potassium amide is used as the metalating agent the submitters report that the same esters may be formed by metalation with sodium amide (43% yield) or with w-butyllithium (39% yield). The latter conditions also yield an appreciable amount of the acid (which decarboxylates). 

In selecfed cases, an improvement of the yield and selectivity has been reported by using an equimolar mixture of lithium diisopropylamide and potassium fer/-butoxide . Similarly to the model seen above, an eight-membered cyclic transition state of type 48 or 49 including the two organometallic species was invoked, as shown in Figure 2 . 

The resulting alkoxyallenes are very prone to racemization under the conditions of the reaction, as well as after isolation. Therefore, contact time with the organometallic reagents should be minimized and the product stored over potassium carbonate. Esterification of the free hydroxy group gives compounds of increased stability107,... 

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