π-Complexes of Phthalocyanines and Metallophthalocyanines

Abstract

Addition of [Cp*Ru(MeCN) 3 ]PF 6 to M(PcOEt) (PcOEt ) octakis(ethoxy)phthalocyanine; M ) H 2 , Ni (1), Cu, VO) in dichloromethane results in the formation of {Cp*Ru[η 6 -M(PcOEt)]}PF 6 . The molecular structure of 1 reveals η 6 -coordination of Cp*Ru 2+ to one of the isoindole subunits of the phthalocyanine ligand. The crystal structure reveals the presence of two cofacially stacked Pc units in the asymmetric unit separated by 3.27-3.36 Å. In [Cp*Ru(η 6 -H 2 PcOEt)]PF 6 , two distinct N-H sites are apparent in the 1 H NMR and IR spectra, but only one is exchangeable. The coordinated macrocycle can be metalated. The UV and electrochemical data indicate that the π-bonded metal center functions as an electron-donating substituent. Luminescence studies indicate that the η 6 -coordination quenches fluorescence to a lesser degree than coordination of metals into the N 4 pocket of the phthalocyanine subunit.

Merging Porphyrins with Organometallics: Synthesis and Applications

“…While studying catalytic hydrodemetalation, Rauchfuss and co-workers realized that the pyrrole rings of the tetrapyrrolic macrocycles could act as h 5 -pyrrolide ligands for p complexes. [137][138][139] Figure 5). The stability of these complexes is related to the electron-donating ability of the porphyrin ring.…”

Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States

“…[2][3][4][5] Transition metals coordinate via  6 -type bonding to the isoindole subunits of the Pc ligands as in {Cp*Ru[ 6 -Ni(PcOEt)]}PF 6 , which was obtained via the interaction of metal octa(ethoxy)phthalocyanine M(PcOEt) (M = H 2 , Ni, Cu, VO) with [Cp*Ru(MeCN) 3 ]PF 6 (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl). 2 In addition, the  5 -type complexes of zinc and nickel octaethylporphyrin with (cymene)Ru 2+ and Cp*Ir 2+ have been obtained and structurally characterized. 3 The transition metal complexes of metal macroheterocycles can also be prepared with metal-metal bonds, such as those observed in phthalocyanine and porphyrin dimers.…”

“…Insoluble-unsubstituted metal phthalocyanines become soluble in organic solvents under reducing conditions, 8 allowing the reaction investigations of metal phthalocyanine radical anions with transition metals. The interactions of (cation + )[Sn IV Cl 2 Pc(3-)] -(cation = Bu 4 N + or cryptand [2,2,2](Na + )) and {cryptand [2,2,2](Na + )}[Sn II Pc(3-)] -(henceforth, cryptand [2,2,2] is abbreviated to cryptand) with transition metal compounds result in the direct coordination of these complexes to tin(II) phthalocyanine to form neutral (1, 2), monoanionic (5-8), and even dianionic (4) coordination complexes, in some of which the spin on [Sn II Pc(3-)] is preserved (5-8, Table 1).…”

Cyclopentadienylruthenium π Complexes of Subphthalocyanines: A “Drop‐Pin” Approach To Modifying the Electronic Features of Aromatic Macrocycles

“…This shift is noticeably larger than that seen with the corresponding phthalocyanine (ca. δ =0.7 ppm shift),16a porphyrin (ca. 1‐1.5 ppm shift),14 or porphycene (ca.…”