Reactivity of bis(pyrazol-1-yl)methanes functionalized by 2-hydroxyphenyl and 2-methoxyphenyl on the methine carbon atom with W(CO)5THF

Reactions of 2-hydroxyphenyl and 2-methoxyphenylbis(pyrazol-1-yl)methanes as well as 2-hydroxyphenyl and 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl)methanes with W(CO)5THF have been carried out. Heating 2-hydroxyphenylbis(pyrazol-1-yl)methane (L1) with W(CO)5THF in THF at reflux yielded complex (L1)W(CO)4.L1, while similar reaction of 2-hydroxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (L2) with W(CO)5THF resulted in the cleavage of a Csp3-N bond to generate 1,2-bis(2-hydroxyphenyl)-1,2-bis(3,5-dimethylpyrazol-1-yl)ethane (L) and pyrazole derivative W(CO)5(3,5-Me2PzH) (Pz = pyrazol-1-yl). These two fragments were connected together through strong O…H–N and O–H…N hydrogen bonds to form complex L.[W(CO)5(3,5-Me2PzH)]2. The analogous results were observed in the treatment of 2-methoxyphenylbis(pyrazol-1-yl)methane (L3) with W(CO)5THF, which gave product L′.[W(CO)5(PzH)]2 (L′ = 1,2-bis(2-methoxyphenyl)-1,2-bis(pyrazol-1-yl)ethane) as well as certain amount of complex (L3)W(CO)4. In addition, during the reaction of 2-methoxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (L4) with W(CO)5THF, partial decomposition reactions took place to yield complexes (L4)W(CO)4 and W(CO)5(3,5-Me2PzH), but no hydrogen bond was found between these two moieties.

Graphical abstractReactions of bis(pyrazol-1-yl)methanes functionalized by 2-hydroxyphenyl and 2-methoxyphenyl on the bridgehead carbon atom with W(CO)5THF have been carried out. Some interesting results are obtained. The cleavage of a Csp3-N bond in these reactions is observed, and the O…H–N and O–H…N hydrogen bonds play an important role in the formation of the final products.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Reactivity of (2-hydroxyphenyl)bis(pyrazol-1-yl)methanes and 2-methoxyphenylbis(pyrazol-1-yl)methanes with W(CO)5THF. ► The cleavage of a Csp3-N bond in bis(pyrazol-1-yl)methane. ► The O…H–N and O–H…N hydrogen bonds. ► Possible formation pathway of complexes.