Anthracene, complex with dichloromethane

Tetranitromethane produces strongly coloured electron donor-acceptor (EDA) complexes with derivatives of the anthracene, in dichloromethane. Specific irradiation of the charge transfer absorption band at X > 500 nm produces a rapid fading of the colour of the solutions. From these solutions, adduct 91 is obtained (reaction 24) its structure is ascertained by X-ray crystallographic diffraction. 91 is derived from an anti-addition of fragments of tetranitromethane by a multistep pathway. ... 

Photochemical osmylation. The irradiation of the charge-transfer bands (Fig. 13) of the EDA complex of 0s04 with various benzenes, naphthalenes, anthracenes, and phenanthrene yields the same osmylated adducts as obtained in the thermal reactions. For example, irradiation of the purple solution of anthracene and 0s04 in dichloromethane at k > 480 nm yields the same 2 1 adduct (B) together with its syn isomer as the sole products, i.e.,... 

The treatment of the bromoacetal (255) with catalytic amounts ( 10%) of a Co(I) species, generated by the electroreduction of cobaloxime (232) in an Me0H-LiCl04 system at —1.8 V, produces the cis-fused adduct (256) in 60 70% yield (Scheme 96) [392]. Cathodic reduction is used for the synthesis of a [Co(CO)3PBu3] complex in a methanol-methyl formate medium, which catalyzes the alkoxycarbonylation of dichloromethane to dimethyl mal-onate in up to 75% yield [393]. The Co(II) complexes are found to be effective for the homogeneous reduction of gem-dichlorocyclopropanes in the presence of anthracene [394]. The formation of the C—C double bond of (258) may be ascribed to the a-elimination of the Co-H species. Thus, benzalchloride (257) can be converted to a mixture consisting primarily of ds- and trans-stilbenes (258) by the action of electrogenerated Co(I)(salen) (Scheme 97) [395-398]. 

Other OTM compounds that are indicated by preliminary studies to be efficient triplet sensitizers include ClRe(C0)2L (Table 12). In dichloromethane at room temperature these complexes are strongly luminescent and photo-inert (41). Under the same conditions, the emissions are quenched by oxygen, anthracene, and trans-stilbene. The trans cis isomerization of trans-stilbene is efficiently sensitized by several of these species. Quantitative sensitization experiments indicated that the luminescing excited states of ClRe(C0)3L are produced with 100 percent... 

The mechanism for the photo-amination is reasonably suggested to involve nucleophilic attack of the amine on to the cation radical of the arene which is generated by photo-induced electron transfer to the dicyanobenzene. Irradiation at wavelengths longer than 500 nm of dichloromethane solutions of the charge-transfer complexes of various anthracenes with tetranitromethane leads to rapid... 

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