In^III‐Phthalocyanine: Darstellung, Eigenschaften und Kristallstruktur von Tetra(n‐butyl)ammonium‐cis‐di(nitrito‐O,O′)phthalocyaninato(2–)indat(III)

Abstract

[In(Cl)Pc2−] bildet mit (nBu4N)NO2 in Aceton grün‐blaues (nBu4N)cis[In(NO2)2Pc2−], welches monoklin kristallisiert (RG.: P21/n (14)). Die Nitrit‐Anionen sind als chelatbildende Nitrito‐O,O′ (NO2)‐Liganden an InIII in cis‐Koordination gebunden. Infolgedessen ist InIII oktakoordiniert und befindet sich in einem verzerrten “quadratischen” Antiprisma auf der dem Pc2−‐Liganden zugewandten Seite. Einer der (NO2)‐Liganden hat ähnlich wie freies Nitrit äquivalente NO‐Bindungen, der andere nichtäquivalente. Beide (In,O,N,O)‐Ringe sind nahezu planar (Diederwinkel: 80°). Der Pc2−‐Ligand ist unsymmetrisch konvex verzerrt. Partiell überlappende Paare einander zugewandter Pc2−‐Liganden bilden von den (NO2)‐Liganden begrenzte Doppelschichten, die von den die (nBu4N)+‐Kationen enthaltenden Schichten getrennt sind. Das Zyklovoltammogramm von cis[In(NO2)2Pc2−]− zeigt drei Elektrodenprozesse, die den Redoxpaaren: Pc3−/Pc2− (−0,94 V) < InI/InIII (−0,78 V) < Pc2−/Pc− (0,64 V) zugeordnet werden. Die UV‐VIS‐NIR‐ und Schwingungsspektren werden diskutiert.

Synthesis, Properties and Crystal Structure of Bis(tetra(n-butyl)ammonium) Bisnitrophthalocyaninatoruthenate(II)

“…The largest perpendicular displacement from the 'best' N p plane is 0.26 Å for C30. The geometry of the pc 2-core and the ( n Bu 4 N) + cation agrees with usual observed values and will not be discussed here [7].…”

“…In agreement with the typical π-π* transitions of the pc 2-ligand, the resonance Raman (RR) spectra resemble those of many other metal phthalocyaninates with D 4h symmetry [7,17]. This is evidenced by two selected RR spectra, displayed in Fig.…”

“…It can serve as a ligand in up to nine different ways [6]. Our preceding investigations on nitrite coordination to metal phthalocyaninates concentrated on the structural characterization of nitrito(O) bonding isomers [7]. In this paper, we report on the synthesis and characterization of stable bis(tetra(n-butyl)ammonium) bis-nitrophthalocyaninatoruthenate(II), (…”

Bis(triphenylphosphine)iminium Nitrito(phthalocyaninato)zincate Hydrate

“…The closest atomic approach between the anions is 3.294(5),~ for the distance between C8 of one Ct• 21 C27 C22 C¢~21 -c29~./~ ""-~ ~c2ol anion and C20 of the other. The Zn-..Zn distance is 6.530 (5) (Gorsch, Franken, Sievertsen & Hornborg, 1995;Assmann, Ostendorp & Homborg, 1995). The geometric data are characteristic for very weak rrrr interactions between the macrocyclic rings (Scheidt & Lee, 1987;Scheidt & Turowska-Tyrk, 1994;Cheng et al, 1994).…”

Unusual catalytic effect of halide anions in the protolytic dissociation of indium(III) octaphenyltetraazaporphyrins

“…Thus, in phthalocyaninatoindium(III) derivatives, the In atom can be six-coordinated in anionic cis-complexes with two fluoride 8 or two cyanate 9 anions (cis-[F 2 InPc]and cis-[(CNO) 2 InPc] -), and has a coordination number of eight in the complex cis-[(NO 2 ) 2 InPc] -. 10 Due to the large ionic radius of In III (r In = 0.81 Å 11 ), transcoordination is not characteristic of its complexes with porphyrins 7 having larger coordination cavities than that of tetraazaporphyrins. The reactive intermediate can be therefore formulated as cis-[(Cl) 3 InOPTAP] 2-(Scheme 1).…”