Gallium alkyls and aryls

The thallium complexes show somewhat different electrochemical behavior, and reversible oxidations are observed for both n-alkyl and n-aryl thallium porphyrins, indicating that the oxidized complexes have a more stable metal—carbon bond than the gallium or indium analogs. Spectroelectrochemistry revealed that the first oxidation is porphyrin ring-centered. The first reduction is reversible and ring... 

The above method has been used for the synthesis of metal alkyl (or aryl) o-bonded porphyrins of iron , cobalt rhodium titanium iridium gallium indium thallium, silicon germanium " " and tin ... 

Other o-bonded metal porphyrins have electronic absorption spectra belonging to the hyperclass. The o-bonded complexes of iron , indium gallium exhibit such typical spectra. Thus, replacement of the anionic axial ligand on the halogenated complexes M(Por)X by an alkyl (or aryl) o-bonded ligand results in a splitting of the Soret band into two bands. One of the bands is red shifted and the other is blue shifted with respect to the same porphyrin complex with anionic axial ligands. This is illustrated in Fig. 2 for In(OEP)Cl and In(OEP)(C(CH3)3). 

The electrochemistry of gallium, indium, and thallium porphyrins with o-bonded aryl and alkyl groups has been reported by Kadish and Guilard . Complexes of Ga(Por)(R), In(Por)(R) and Tl(Por)(R) are reversibly reduced by up to two single electron transfer additions. These electroreductions are shown in Eq. 12 and 13 where M = Ga, In, or Tl. 

The insertion of sulfur dioxide between the metal atom and the alkyl or aryl group of indium gallium and iron porphyrins of the form M(Por)(R) gives rise to M(Por)S02R sulfinato derivatives (Eq. 18). The iron sulfinato compounds are air stable at room temperature, but can easily be oxidized by a stream of oxygen to give the corresponding sulfonato complexes. 

No monomeric alkali metal alkyls or aryls are known, as those crystal structures which have been determined indicate electron-deficient, e.g. (MeLi), or ionic (K Me ) constitutions. The dialkyls of the lighter second group metals are mostly electron-deficient dimers or polymers, but those of zinc, cadmium and mercury are monomers with a linear structure as expected from participation of one (metal) s and one p orbital (with or without dji participation). In the third group the pattern is more complex. Whereas the trialkylboranes are monomeric, boron hydrides (and alkyl hydrides) and polyboron compounds form electron-deficient structures. Aluminium alkyls and alkyl hydrides are normally electron-deficient dimers or trimers gallium trialkyls are monomeric though the trivinyl is a dimer trimethylindium is a weakly associated tetramer in the solid state, otherwise all indium and thallium trialkyls appear to be monomers. 

Triflates of boron, aluminum, and gallium were found to be efficient catalysts in Friedel-Crafts acylations.46 However, these are water-sensitive materials and were required to be used in equimolar quantities to be effective. More recently various water-tolerant and recyclable triflate salts, which were also tested in alkylation, were found to exhibit similar good characteristics in Friedel-Crafts acylations. Although benzene cannot be acylated, Sc triflate,47 48 lanthanum triflates,48-51 and Hf triflate52 usually give high yields of aryl ketones in acylation with acid anhydrides. In many cases, Li perchlorate was found to accelerate the reactions.48 52... 

Gallium(III) triflate catalysed the rearrangement of 2-substituted vinyl epoxides into /3,y-unsaturated carbonyl compounds with high regio- and chemo-selectivity with low catalyst loading. Alkyl-substituted trimethylsilylvinyl epoxides gave /i,y-unsaluralcd ketones, but aryl-substituted vinyl epoxides gave the aldehydes.80... 

Tris[ (l S,2i )-6,6-dimethylbicylo[3.1.1]heptan-2-yl methyl]gallium reacts with ketones above room temperature, and optically active alcohols are obtained as main products (Scheme 145).438 LiGaH4, in combination with an S,0-chelate ligand, 2-hydroxy-2 -mercapto-l,T-binaphthyl (MTBH2), forms an active hydride catalyst for an asymmetric reduction of prochiral ketones with catecholborane. Enantiofacial differentiation is based on the steric requirement of the ketone substituents. Aryl//z-alkyl ketones are reduced in 90-93% ee and branched ketones RC(0)Me (e.g., R = Pr , oC6H11 Bu ) in 60-72% ee (Table 43).439 440... 

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