Double‐Decker Ferrocene‐Type Complex of N‐Fused Porphyrin: A Model of π‐Extended Ferrocene?

Abstract

Whopper sandwich: A double‐decker ferrocene‐type complex with N‐fused porphyrinato ligands (see picture) was synthesized from N‐fused porphyrin, and its structure and properties were characterized with X‐ray crystallographic analysis, variable‐temperature 1H NMR spectra, and electrochemical measurements. The unique three‐dimensional d–π conjugated system was elucidated with the aid of DFT studies.

η5‐Cyclopentadienyliron(II)–[14]Triphyrin(2.1.1) Sandwich Compounds: Synthesis, Characterization, and Stable Redox Interconversion

“…The distances between Fe II ion and the four meso ‐carbon plane of complexes 2 a and 2 b are (1.483±0.013) and 1.422 Å, which are much more shorter than those of the previously reported metallotriphyrin complexes: 1.825 Å for [Re I (TriP)(CO) 3 ], 1.678 Å for [Ru II (TriP)(CO) 2 Cl], and 1.631 Å for [Pt IV (TriP)Cl 3 ]. The average FeN bond lengths are 1.894–1.897 Å for 2 a and 1.895 Å for 2 b , respectively, which are similar to [Fe II (NFP) 2 ] 7…”

“…Especially in porprhyin families, there are a few reports in this context:3 1) Cp‐Sc III ‐porphyrin,4a Cp‐Zr II ‐porphyrin,4b and Cp*‐Ru IV ‐porphycene (Cp*=pentamethylcyclopentadienyl),4c although porphyrin and porphycene are divalent ligands; and 2) β,β′‐fused monoruthenocenylporphyrins, bisferrocenoporphyrins,5a metaloporphyrcenes,5b and cyclopentadienylruthenium π complexes of subphthalocyanines,5c where that five‐membered ring moiety (pyrrole or cyclohexadiene moiety) acted as ligands. Only recently, double‐decker iron(II) complexes of dithiaethyneporphyrin6 and N‐fused porphyrin (NFP),7 where they behaved as macrocyclic tridentate ligands with a single negative charge, have been reported. During the synthesis of NFP complex, the Cp‐Fe II ‐NFP compound was detected by mass spectroscopy; this compound has yet to be isolated.…”

Regioselective addition/annulation of ferrocenyl thioamides with 1,3-diynes via a sulfur-transfer rearrangement to construct extended π-conjugated ferrocenes with luminescent properties

“…S7 †). 48 Although fused ferrocenes have been studied widely, [49][50][51][52][53] the ring-fused strategy is herein employed for the rst time to construct luminescent materials based on ferrocenes, which would give us inspiration for the development of novel organic optoelectronic materials, such as electroluminescent materials based on ferrocenes.…”

N-Fused Porphyrin: A Maverick Member of the Porphyrin Family

“…While an effort to obtain a hybrid of N-fused porphyrin and ferrocene (compound 10) has failed so far, a double-decker iron(II) complex of N-fused porphyrin (9) was unexpectedly obtained in 14% yield by heating of N-fused porphyrin with [FeCp(CO) 2 ] 2 (Scheme 10). 29 A hybrid-type complex was successfully obtained in the case of ruthenocene (Scheme 11). 30 The thermal reaction of N-fused porphyrin with [RuCp(CO) 2 ] 2 gave the hybrid of ruthenocene and N-fused porphyrin (11) in an expected manner.…”