ISSN:
0044-2313
Keywords:
Magnesium compound
;
phthalocyanine complex
;
crystal structure
;
vibrational spectra
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc2-]- (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone SolvateMagnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((nBu4N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc2-]-; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (nBu4N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of b(PNP)[Mg(Cl)Pc2-] · CH3COCH3 reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (Niso) of the nonplanar Pc ligand toward the Cl atom (d(Mg—Ct) = 0.572(3) Å; d(Mg—Cl) = 2.367(2) Å). The average Mg—Niso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (b(PNP)+: d(P1—N(K)) = 1.568(3) Å; d(P2—N(K)) = 1.587(3) Å; ∡(P1—N(K)—P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.
Notes:
Magnesiumphthalocyanin reagiert mit überschüssigem Tetra(n-butyl)ammonium- oder Bis(triphenylphosphin)iminiumhalogenid ((nBu4N)X oder (PNP)X; X = F, Cl, Br) zu Halogenophthalocyaninatomagnesat ([Mg(X)Pc2-]-; X = F, Cl, Br), welches teilweise als wenig lösliches (nBu4N)- oder (PNP)-Komplexsalz kristallisiert. Die Kristallstrukturanalyse von b(PNP)[Mg(Cl)Pc2-] · CH3COCH3 bestätigt die tetragonal-pyramidale Koordinationsgeometrie des Mg-Atoms, wobei dieses aus dem Zentrum (Ct) der inneren vier Stickstoffatome (Niso) des nicht-planaren Pc-Liganden in Richtung des Cl Atoms verschoben ist (d(Mg—Ct) = 0,572(3) Å; d(Mg—Cl) = 2,367(2) Å). Der mittlere Mg—Niso-Bindungsabstand beträgt 2,058 Å. Im festen Zustand bilden je zwei Anionen partiell überlappende Dimere. Das Kation liegt in gewinkelter Konformation vor (b(PNP)+: d(P1—N(K)) = 1,568(3) Å; d(P2—N(K)) = 1,587(3) Å; ∡(P1—N(K)—P2) = 141,3(2)°). Elektrochemische und spektroskopische Eigenschaften werden diskutiert.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220625
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