Quinones with organometallic

Amouri, H. Vaissermann, J. Rager, M. N. Grotjahn, D. B. Rhodium-stabilized o-quinone methides synthesis, structure, and comparative study with their iridium congeners. Organometallics 2000, 19, 5143-5148. 

Factors affecting whether quinones undergo addition or reduction hr their reactions with some organometallics, and with HN3, are discussed under Redox Reactions later. 

Reaction of organometallics such as alkyllithiums or Grignard reagents with p-quinones can give an addition product, or a hydroquinone (i.e. reduction product). The... 

Addition to quinone monoketals and quinol ethers.2 Complexation of quinone monoketals or quinol ethers with MAD permits 1,4-addition of organo-lithium and Grignard reagents. Highest yields obtain with aryl, vinyl, and acetylenic organometallics. 

There are very few examples of MOFs that have organometallic complexes as metalloligands, or so-called organometalloligands . However, Sweigart and co-workers (139-144) studied a number of such compounds. Their organo-metalloligand of choice was the piano stool complex [(Tj -benzoquinone)Mn (CO)3] , or /i-QMTC (Fig. 33). The C=0 moieties of the quinones can associate to secondary metal centers to form supramolecular networks with a rich diversity of... 

Thus this system generates the reducing radical CHjOH so that when the solubility of a compound is higher in methanol than in water it is advantageous to effect its one-electron reduction by the radiolysis of its methanolic solution. This technique has been utilised, for example, for one-electron reduction of some organometallic complexes and quinones. As in water, e " can be converted to CHjOH via reactions (19) (with N2O) and (29) ... 

Lee et al. found that the DABCO-catalyzed MBH reaction between methyl acrylate and methyl vinyl ketone with 2,3-dihalo-1,4-naphthoquinone 60 forms a-vinylnaphthoquinones in moderate to good yields. The same authors subsequently reported additional examples of the use of DABCO attached enolate anion of methyl acrylate and MVK in substitution reactions of halo-quinones to form a-vinylquinone bonds, avoiding the use of organometallic reagents (Scheme 2.26). ... 

---