Phthalocyanines with phosphonate moiety viaC-nucleophilic substitution in phthalonitriles

Interaction of isomeric 4-nitro- or 3-nitrophthalonitrile with triethyl phosphonoacetate, diethyl cyanomethylphosphonate or tetraethyl methylenediphosphonate in basic conditions resulted in regioselective C -nucleophilic oxidative substitution of hydrogen ortho-located to nitro group, new phthalonitriles with diethoxyphosphorylmethyl or bis(diethoxyphosphoryl)methyl group were isolated in modest yields. In the same conditions one chlorine atom of tetrachlorophthalonitrile was regioselectively substituted with triethyl phosphonoacetate. In basic conditions, both parent phthalonitriles and corresponding zinc phthalocyanines with ortho-located nitro and diethoxyphosphoryl substituted methyl groups are involved in reversible acid-base interaction accompanied with large bathochromic shift of their long wavelength absorption maxima in visible or NIR region, correspondingly. Formation of tetraazachlorin- and tetraaza(iso)bacteriochlorin-like anions is proposed for explanation of this unprecedent bathochromic shift for phthalocyanines.

Remote and α-Thio Carbene Complexes Derived from an Oxazolinylsubstituted Thiophene

Transmetallation and oxidative substitution were utilized to prepare examples of group 14, group 6 and group 10 complexes from lithiated or chlorinated 4,4-dimethyl-2-(2-thienyl) oxazoline or its N-alkylated analogs. Two of the product types (2and 5) can be classified as a-thio or remote carbene complexes, depending on the position (3- or 5-) of attachment to the substituted thiophene ring. Spectroscopic measurements as well as crystal and molecular structure determinations clarified the bonding within the new compounds.