Dialkyl species

A number of examples have been reported documenting the use of palladium phosphine complexes as catalysts. The dialkyl species [PtL2R2] (L2 = dmpe, dppe, (PMe3)2 R = Me, CH2SiMe3) catalyze the reaction of [PhNH3]+ with activated alkenes (acrylonitrile, methyl acrylate, acrolein).176 Unfunctionalized alkenes prove unreactive. The reaction mechanism is believed to proceed via protonation of Pt-R by the ammonium salt (generating PhNH2 in turn) and the subsequent release of alkane to afford a vacant coordination site on the metal. Coordination of alkene then allows access into route A of the mechanism shown in Scheme 34. Protonation is also... 

A disadvantage of borane and borate systems is that the alkylmetallocene cations are more instable and more sensitive to impurities and water. To overcome this higher sensitivity, a dialkyl species can be build by an in situ reaction with tri-isobutylaluminum (TIBA). TIBA acts as alkylation reagent and as a scavenger and stabilizes the dialkyl species in solution it is used as stock solution for the polymerization experiments (Fig. 12). 

There has been little insight into potential decomposition pathways for the Ni(II) system due to sparse experimental evidence. Polymerization results with catalysts bearing different alkyl and fluorinated substituents have suggested that a C-H activation process analogous to that occuring with the Pd(II) catalysts is unlikely with Ni(TT) [28], Instead, side reactions between Ni and the aluminum coactivator, present as it is in such large excess, have been implicated. The formation of nickel dialkyl species and their subsequent reductive elimination to Ni(0) is one possible deactivation mechanism [68]. 

Among the group 16 elements, mostly non-metallic ones like TeCl were examined [11]. The reaction with TeCU proceeds in a stepwise manner giving the mono-alkyltellurium and the dialkyl compound in accordance with the stoichiometry of the reagents Eq. (21). As in the case of tin and bismuth, the second alkylation is much slower than the first and the dialkyl species could not be alkylated any further. 

Keys to the high polymerization activities of single-site catalysts are the cocatalysts. MAO is most commonly used and is synthesized by controlled hydrolysis of trimethyl aluminum. Other bulky anionic complexes which show a weak coordination, such as borates, also play an increasingly important role. One function of the cocatalysts is to form a cationic metallocene and an anionic cocatalyst species. Another function of MAO is the alkylation of halogenated metallocene complexes. In the first step, the monomethyl compound is formed within seconds, even at -60°C (69). Excess MAO leads to the dialkylated species, as shown by NMR measurements. For the active site to form, it is necessary that at least one alkyl group be bonded to the metallocene (70). 

Cyclopropen-1-yl sodium derivatives are also readily prepared. Thus reaction of cyclopropene with one equivalent of sodium amide in liquid ammonia leads to 1-sodiocyclopropene which is alkylated by haloalkanes 77,78 reacts with ketones to produce tertiary alcohols and opens epoxides to produce 2-cyclopropenyl-ethanols in moderate to good yields79). Moreover, on reaction with two equivalents of base followed by haloalkane, 1,2-dialkylated species are obtained sequential reactions can also be used to produce unsymmetrically substituted cyclopropenes78). Reaction with a deficiency of sodium amide can also cause addition of the cyclopro-penyl anion to unreacted cyclopropene, leading to products derived from the 2-cyclo-propylcydopropen-l-yl anion and to 1,2-dicyclopropylcyclopropene 77). 

Activities no greater than that of morphine have been observed in benzo-morphans bearing 2-, 4-, or 5-substituents, and in general, substitution in these positions tends to reduce responses in 6-alkyl and 6,11-dialkyl species (p. 193). 

In the atmosphere, TAL is decomposed photocat-alytically by ultraviolet irradiation, by ozone, or by hydroxyl radicals to the more stable, water-soluble ionic tri- and dialkylated species. Monoalkyl-lead cations are assumed to be very unstable. The... 

The synthesis of a new family of monoanionic, tridentate bis(imino)carbazolide ligands and their iron complexes has been reported. Treatment of 92a with MeLi affords the Fe(ni) dialkyl species 92b, whose magnetic moment of 1.8/iB suggests a low-spin configuration (Scheme 16). Alkylation of the Fe(ll) bis(imino)carbazolide monochloride precursor leads to four-coordinate monoalkyl 93, displaying a magnetic moment of 3.0... 

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