ISSN:
0044-2313
Keywords:
Phthalocyaninates(2-)
;
ruthenium compounds
;
iron compounds
;
vibrational spectra
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis, Properties, and Crystal Structure μ-Carbidodi(pyridinephthalocyaninato(2-)iron(IV)) and -ruthenium(IV))Soluble μ-carbidodi(pyridinephthalocyaninato-(2-)iron(IV)) and -ruthenium(IV) is prepared as a pyridine solvate, [{M(py)pc2-)2(μ-C)] · py (M = Fe, Ru) by the reaction of μ-carbidodi(phthalocyaninato(2-)iron(IV)) and -ruthenium(IV)) with pyridine. The isotypic complexes crystallize in the orthorhombic space group P212121 (No. 19) with lattice parameters (in Å): a = 12.692(3)713.002(3) (Fe/Ru); b = 22.186(2)722.635(6); c = 23,653(2)/23.901(6). The M atoms are virtually in the centre (Ct) of the (Np)4 plane (d(M-Ct) = 0.039(6)70.054(8) Å; Np: pyrrole-N atom). The averaged (M-Npy) distance (py: pyridine) is 1.94(1)/2.010(8) Å. The M-(μ-C)-M core is almost linear. The (M-(μ-C)) distance is 1.69(2)71.77(1) Å. The pc2- ligands are in a hitherto unknown convex staggered conformation. The asymmetric (M-(μ-C)-M) stretching vibration is observed in the IR spectrum at 9117974 cm-1, while the corresponding symmetric one is selectively enhanced only in the RR spectrum at 477 cm-1 of the iron complex.
Notes:
Lösliches μ-Carbidodi(pyridinphthalocyaninato(2-)eisen(IV) und -ruthenium(IV) wird durch die Umsetzung von μ-Carbidodi(phthalocyaninato(2-)eisen(IV) und -ruthenium(IV) mit Pyridin als Pyridin-Solvat, [{M(py)pc2-}2(μ-C)] · py (M = Fe, Ru) isoliert. Die isotypen isotypen Komplexe kristallisieren orthorombisch in der Raumgruppe P212121 (Nr. 19) mit den Gitterkonstanten (in Å): a = 12,692(3)/13,002(3) (Fe/Ru); b = 22,186(2)/22,635(6); c = 23,653(2)/23,901(6). Die M-Atom befinden sich fast im Zentrum (Ct) der (Np)4-Ebene (Np: Pyrrol-N-Atom): d(M-Ct) = 0,039(6)/0,054(8) Å. Der mittlere (M-Np)-Abstand beträgt 1,94(1)/2,010(8) Å. Die (M-(μ-C)-Abstand beträgt 1,69(2)/1,77(1) Å. Die pc2--Liganden sind in einer bislang unbekannten komplexen Staffel-Konformation einander zugeneigt. Die asymmetrische (M-(μ-C)-M)-Valenzschwingung liegt im IR-Spektrum bei 911/974 cm-1, die symmetrische beobachtet man dagegen nur im RR-Spektrum des Eisen-Komplexes bei 477 cm-1.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.199762301151
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