Lanthanoid amides

Table VI.l. Lanthanoid amides, mixed halide/amides and similar complexes.

Ytterbium triflate [Yb(OTf)3] combined with TMSG1 or TMSOTf are excellent reagents for the conversion of a-methyl styrene and tosyl-imines into homoallylic amides 32 (Equation (19)) (TMS = trimethylsilyl).29 These conditions produce the first examples of intermolecular imino-ene reactions with less reactive imines. Typically, glyoxalate imines are necessary. A comprehensive examination of the lanthanoid metal triflates was done and the activity was shown to directly correlate with the oxophilicity scale. The first report used preformed imines, and subsequently it was found that a three-component coupling reaction could be effected, bypassing the isolation of the intermediate imine.30 Particularly noteworthy was the successful participation of aliphatic aldehydes to yield homoallylic amines. 

NOPC12H12, Phosphinic amide, diphenyl-lanthanoid complexes, 23 180 NOPSiCi2H]9, Phosphinimidic acid, P-methyl-F-phenyl-iV-(trimethylsilyl)-2,2,2-trifluoroethyI ester, 25 72 NOSSiCsHj, Silanamine, 1,1,1-trimethyl-iV-sulfinyl-, 25 48... 

HEXAKlS(DIPHENYLPHOSPHINIC AMIDE)LANTHANOID(III) HEXAFLUORO PHOSPHATES,... 

The hexafluorophosphate ion has proved to be very useful for studies with complexes, since the [PF6] anion has a very weak coordinating ability.1 Lan-thanoid hexafluorophosphates can be obtained in very concentrated aqueous solutions by reaction of a freshly prepared solutions of hexafluorophosphoric acid and a hydrated lanthanoid basic carbonate.2 The resulting solution, after filtration, is evaporated to near dryness. Attempts to isolate the hydrated salts are unsuccessful because of decomposition accompanied by hydrogen fluoride evolution. Nevertheless, the complexes containing diphenylphosphinic amide are isolable and are quite stable.3... 

PC8HM, Phosphine, dimethylphenyl-, 22 133 iridium complex, 21 97 PC 2H27, Phosphine, tributyl-, chromium complexes, 23 38 PC18H1S, Phosphine, triphenyl-, 21 78 23 38 cobalt complexes, 23 24-25 cobalt, iridium, and rhodium complexes, 22 171, 173, 174 iridium complex, 21 104 palladium complex, 22 169 palladium and platinum complexes, 21 10 ruthenium complex, 21 29 PNOC 2Hl2, Phosphinic amide, diphenyl-, lanthanoid complexes, 23 180 PNAH.2, Propionitrilc, 3,3, 3 -phosphinidy-netri-,... 

The naphthalene complexes CioHgLn(THFX are the suitable precursors for lanthanoid (II) amides. As has been shown with naphthaleneytterbium these derivatives readily react with R2NH to give (R2N>2Ln in a high yield [1]. 

The silylamides of lanthanoids(III) are formed in a good yield in the reactions of REM chlorides with lithium bis(trimethylsilyl)amide [3, 5]. 

The tris(silylamide) complexes, [(Me3Si)2N]3Ln, are isolated from a pentane solution as needle crystals readily hydrolysed on air. They are well soluble in common organic solvents and posses a rather high volatility. These properties as well as the simplicity of their synthesis and the high reactivity of Ln-N bonds make REM amides one of most suitable starting material for the preparation of other organic and inorganic compounds of lanthanoids. The last method can be used as well for the preparation of mixed chloride/amides of lanthanoids [29]. 

Table VI.2. Mixed cyclopentadienyl/amides of lanthanoids and relative complexes.

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