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.

b) for the use ofchiral ammo acids to control the helicity of ferric ion hinders. see. 1. Libman. Y. Tor, A. Shanzer, J. A m .Interactions between transition metals and heterocycles are relevant to many areas of science and technology. This topic has elicited recent interest in the context of hydrotreating catalysis, the industrial process by which heteroatom-containing contaminants are removed from fossil fuels.['] Studies to date have

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Eine neue Bindungsweise liegt in der Titelverbindung vor, einem Sandwich‐Komplex, in dem ein Metalloporphyrin als π‐Ligand eines Metallocens fungiert. Sowohl die röntgenographisch ermittelte Struktur (siehe Bild rechts) als auch spektroskopische Ergebnisse machen deutlich, daß die Eigenschaften der Metalloporphyrineinheit stark durch die Komplexierung verändert werden.magnified image

Diastereomeric iminium thiolato complexes were prepared by the addition of S-(−)-α-methylbenzylamine to the π-thiophene complexes [(C6Me6)Ru(2-RC4H3S)]2+, where R = Me (1 2+), CH2OH (3 2+), and 2-C4H3S (6 2+). After chromatographic separation, the diastereomers were treated with HOTf to generate optically pure π-thiophene complexes. The absolute configuration of [(C6Me6)RuSCMeC2H2(CHNHCHMePh)]OTf, (−)-2(OTf), was determined by a single-crystal X-ray diffraction; the monohydrate crystallized in the acentric space group P212121. Acetone solutions of (−)-1 2+ and (−)-3 2+ are optically stable for days in solution (25 °C), while the bithiophene complex was unstable with respect to dissociation of the bithiophene ligand. Optical resolution of [(cymene)Os(2-MeC4H3S)](OTf)2 was not possible due to the instability of the iminium thiolato. Base hydrolysis of (−)-1 2+ gave the formyl thiolato complex (−)-9 kin, which isomerized to (+)-9 therm with inversion of configuration at Ru, as indicated by circular dichroism measurements. The methyl ester of the amino acid (l)-phenylalanine was shown to add to (C6Me6)Ru(C4H4S)2+ to give a 2:1 mixture of diastereomeric iminium thiolato complexes.