Reaction of triphenylphosphine with copper complexes derived from 2-nitrosophenols (1,2-quinone mono-oximes)

Reactivity of 1‐Nitroso‐2‐naphthol Towards the Carbonyl Complexes XRe(CO)5 (X = Cl, Br, I): Molecular Structures of cis‐[η2‐{N,O‐C10H6ON(O)}Re(CO)4] and fac‐[η2‐{N,O‐C10H6ON(H)}Re(CO)3X]

“…In the case of 3, this observation can be rationalised by considering two mesomeric forms of 1-nitroso-2-naphthol (Scheme 2). The short C-N bond lengths of 4-6 can be explained as a result of the reduction due to CO forming the quinoid sys- [17] and cis-[Ru{η 2 -N(O) C 10 H 6 O} 2 (CO) 2 ] (1.258 Å). [21] The dihedral angles N( …”

“…[13,14] Metal complexes derived from 1,2-naphthoquinone-monoimines can also be employed as starting reagents in the synthesis of a wide variety of organic compounds. [15][16][17] It is well known that nitro and nitroso compounds can be reduced to give products via the formation of imido intermediates. In 1975 Saarinen et al published the X-ray structure of a copper complex with the 1-nitroso-2-naphthol ligand, which was followed by a report by Charalambous et al in 1983.…”

The Synthesis and Utility of Metal-Nitrosophenolato Compounds—Highlighting the Baudisch Reaction

“…The yields varied (Figure 12), but products were easily separated from starting material. This reaction is different to those which lead to a O , N -diheterocycle in the cycloaddition processes, as only the N -containing functional groups are involved and the hydroxyl groups are outside the newly formed ring [77]. The reported yields were similar starting from either the free nitrosophenol or copper-nitrosophenolato complex.…”

“…Pathways to more complex structures starting from copper-nitrosophenolato complexes have been shown in a study by Charalambous et al [35,77,78], who were aiming to prepare nitrene metal complexes via deoxygenation of 2-nitrosophenols with PPh 3 . While nitrenes were proposed intermediates in the reported reactions, they were not the isolated products.…”

“…The conditions and reagents required are much the same as per those for the aforementioned cycloaddition, with one important difference: the reaction is performed in anhydrous solvent (methanol). The possible mechanism was not elaborated and does not appear to have been revisited since; however, it was thought to be comparable to the reduction-nitrene-formation observed in the phenazine synthesis [75,77]. The reaction time is fairly short (1 h), but forcing conditions were required (Scheme 11).…”