Germyls metal

Phosphonium salts of anionic trihydridogermyl metal carbonyl complexes for V, Nb, Cr, Mo, W, Mn, Re, Co and Ni have been synthesized by substitution of carbonyl group with trihydrido germane, —GeH3 " (equation 9). Hydridogermyl metal complexes are the precursors for metal germylenes and polynuclear metal germyl complexes . 

Germyl, Stannyl, and Plumbyl Anions The preparative methods for the synthesis of the germyl, stannyl, and plumbyl anions are essentially the same as those mentioned above for the silyl anions. The most widely used methods are (1) reduction of halides R3EX (R = alkyl, aryl E = Ge, Sn, Pb X = Cl, Br) with alkali metals and (2) reductive cleavage of the E-E bond of R3E-ER3 (R = alkyl, aryl E = Ge, Sn, Pb) with alkali metals or organolithium reagents. Due to the favorable polarization of the (E = Ge, Sn, Pb) bond, the direct metalation... 

Ge—metal bonds can be built in analogy as described for Ge—C bonds by the reaction of organolithium compounds with metal halides. With trans-dichlorobis(triethylphosphine)platinum(II), new germyl transition metal complexes were synthesized (equation 36)41. 

The Ge-Ge bond can undergo cleavage in reactions with [Bu4N]F to yield metal-free germyl anions, which can be employed in subsequent reactions with alkyl halides (Equation (210), Table 27) and carbonyl species (Equation (211), Table 28).266... 

Silicon and germanium hydrides react with cobalt, manganese and rhenium carbonyls affording complexes having a silicon (or germanium)-metal bond. These reactions, described previously for inactive compounds have been used in the synthesis of optically active silyl and germyl-transition metals ... 

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

By no means do all metallocarboranes have the metal atoms occupying vertices of the basic polyhedra. Apart from many derivatives in which o-bonded metal residues occupy exo sites attached to particular skeletal atoms, several metalloboranes and -carboranes are known in which the metal occupies an edge-bridging site, effectively replacing a bridging hydrogen atom of the parent borane. Many are nido species related to BeHio, for example, the /x-silyl and /i-germyl carboranes. 

Besides couplings through metal atoms observed in such compounds as 73 in which 3/(PSndy3) = 44 Hz,<1968,95) the most interesting data come from the germyl and silyl homologs of the P111 compounds discussed earlier. 

Entry 3 constitutes the first reported example of a metal vinylidene-mediated reaction involving a 1,2-germyl migration. The formation of germylated product is extremely rapid, in agreement with the high reactivity of alkynylgermanes. Both Au(III)- and Au(I)-salts catalyze the observed reaction therefore, a Au(I)-vinylidene mediated reaction mechanism is favored (Scheme 9.24). 

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