Tetrakis(diethyl‐phosphonat)‐, Tetrakis(ethyl‐phenylphosphinat)‐ und Tetrakis(diphenylphosphin‐oxid)‐substituierte Phthalocyanine

Abstract

Tetrakis(diethyl phosphonate), Tetrakis(ethyl phenylphosphinate)-, and Tetrakis(diphenylphosphine oxide)-Substituted PhthalocyaninesThe title compounds 7, 9, and 11 are obtained by tetramerization of diethyl (3,4-dicyanophenyl)phosphonate (5), ethyl (3,4-dicyanophenyl)phenylphosphinate (8), and 4-(diphenylphosphinyl)benzene-1,2-dicarbonitrile (10). The 31 P-NMR spectra of the phthalocyanines 7, 9, and 11 and of their metal complexes present five to eight signals confirming the formation of four constitutional isomers with the expected C 4h , D 2h , C 2v , and C s symmetry. In the FAB-MS of the Zn, Cu, and Ni complexes of 7 and 9, the peaks of dimeric phthalocyanines are observed. By gel-permeation chromatography, the monomeric complex [Ni (7)] and a dimer [Ni(7)] 2 can be separated. These dimers differ from the known phthalocyanine dimers, i.e., possibly the P(O)(OEt) 2 and P(O)(Ph)(OEt) substituents in 7 and 9 are involved in complexation. The free phosphonic acid complex [Zn (12) (12)], only the peaks of the dimer are present; the ESI-MS confirms the existence of the dimer and the metal-free dimer. In the UV/VIS spectrum of [Zn(12)], the hypsochromic shift characteristic for the known type of dimers from 660 ± 700 nm to 620 ± 640 nm is observed. As in the FAB-MS of [Zn(12)], the free phosphinic acid complex [Zn(13)] shows only the monomer, an ESI-MS cannot be obtained for solubility problems. The UV/VIS spectrum of [Zn(13)] demonstrates the existence of the monomer as well as of the dimer.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric {[10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated {[10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2]}

“…After treatment of 15 and 16 with excess pyridine, the ν̃(PO) value for the isolated solids indicates the presence of uncomplexed phosphine oxide ligand. Interestingly, Märkl and co-workers did not observe such a self-coordination feature for their zinc phthalocyanine . The chemical shifts in the 31 P NMR spectra, between 29.2 and 35.7 ppm, also agree well with the values reported for the phthalocyanines.…”

“…Phosphine oxides are well-established ligands for a variety of purposes and are, for example, an integral part in the removal of radioactive waste from solutions . Although there has been one report where a phosphine oxide has been directly attached to a phthalocyanine, no such examples exist for porphyrins. The formation of a phosphine oxide attached to the meso position of an octaethylporphyrin via a methylene spacer was observed by us during an attempt to obtain an ylide from a porphyrinylmethylphosphonium iodide, while a Japanese group reported a phosphine oxide attached to a porphyrin via a biphenyl spacer group.…”

Surface Modification Using Phosphonic Acids and Esters

“…For instance Buchwald et al, Fu et al , and Ogawa et al have replaced palladium with copper with good success. On the other hand, the use of nickel has also been considered − but in that case relatively harsh conditions are required for this reaction (high temperature over 150 °C).…”

Synthesis of substituted phthalocyanines

“…Similarly, cyclotetramerization reactions of diethyl (3,4-dicyanophenyl)-phosphornate with organic base (DBU) in ethanol results in formation of metal-free 2,9(10), 16(17),23(24)-tetrakis(diethylphosphonate)phthalocyanine. 181 All of these phthalocyanines can be hydrolyzed in high yields to give the corresponding phosphoric acid derivatives.…”