Germyl lithium

We have discussed the direct formation of anions by reaction of silyl- or germyl-lithiums with metal carbonyls (cf. Sect. 2.12) ... 

The reaction of [Mn(CH3)(CO)5] with Na[M(CO)5] (M = Mn, Re) followed by CH3OSO2F gives bimetallic carbene complexes [(CO)sMMn- C(0CH3)(CH3) (C0)4] (90). The reaction of [Mn(CH3)(CO)s] with OH followed by allyl bromide led to the formation of [Mn(i7 -C3H5)(CO)4] and reductive elimination of methane (91) (Scheme 7). The reaction of [Mn(CH3)(CO)5] with germyl lithium species gave anionic compounds [Eq. (28)] which were either isolated as tetraethylammonium salts or al-... 

Reaction with germyllithiutn reagents can yield CO inserted products (92) [Eq. (54)]. Thus methyl rheniumpentacarbonyl reacts with germyl-lithium compounds to give anionic acyl complexes which can be isolated as tetraethylammonium salts or alkylated to give carbene complexes. 

Acylgermanes are prepared by the reaction of ester with germyl lithium reagents (Scheme 11.56) [82]. 

A very original synthesis providing germyl-substituted ferrocenes 7 involves organo-lithium compounds33,34 (Scheme 5). 

The reactions with germyl iodides were carried out at — 78° with dimethyl ether as solvent. To obtain good yields, the dilithium telluride must be free of ammonia and lithium amides2. 

Lithium ethanetellurolate condensed with silyl chlorides and with triethylgermyl chloride to form ethyl silyl (germyl) tellurium compounds6. 

Reaction of methanetellurol with lithium aluminum hydride in diethyl ether caused liberation of hydrogen and formation of lithium tetrakis[methyltelluro]aluminate. This compound was not isolated but reacted with silyl or germyl halides to give silyl or germyl methyl tellurium derivatives4. 

Lithium tetrakis[methyltelluro]aluminate, prepared from methanetellurol and lithium aluminum hydride, reacted with silyl, germyl, and stannyl halides at low temperatures to produce, for instance, methyl silyl tellurium derivatives1. 

Germylated ynamines 47 can be obtained in the same fashion from lithium ynamines... 

Freshly prepared lithium wire, and selenium and tellurium powders were used as supplied. Germyl fluoride may be prepared from germyl iodide11 and lead(II) fluoride.12 Chlorotrimethylsilane is distilled through traps at -45° (chlorobenzene-liquid N2 slush), -78° (methanol-dry ice slush), and -196° (liquid N2) the fraction retained in the trap at -78° is the desired purified chlorotrimethylsilane. Peroxide-free diethyl ether was distilled in a vacuum system from fresh Li[AlH4] and stored in vacuo. Caution. The use of Li[AlHA] for drying ethers can lead to explosions 3 Commercial dry NH3 (10-15 mL portion) was further dried by condensation onto Na pellets (about 1 g) in an ampul (about 50 mL) held at -78° on the vacuum line. After 30 minutes the dried NH3 was pumped from the ampul and degassed in a trap held at -196° before use. 

In a series of papers, Itoh and Mikami have reported the high yield, radical a-trifluoro-methylation of ketones using titanium euolates and Mefl/BEts as free radical generator and trifluoromethylating agent . The use of excess Ida and Ti(OPr-/)4 in the preparation of the titanium euolate represeuts the key to the success of the reaction (equation 41). Interest in this reaction stems from the fact that in general, the radical a-trifluoromethylation of ketones via lithium enolates is complicated by the easy defluorination of the a-CFs ketone by the parent enolate . For this reason, less reactive enolates such as silyl or germyl enolates have been initially used instead of lithium enolates" . 

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