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INTRODUCTION; MONOMETALLIC
PORPHYRINS
338
J. W. BUCHLER
BIMETALLIC PORPHYRINS
Some other unusual geometries and stoichiometries were
discussed previously [7], namely the bimetallic complexes
L and P (molar ratio M/(p) = 2:1). Solutions and spectra of
the former M2(p) containing the univalent metals M Ag,
Li, Na and K have been known for a long time; however,
crystalline phases of alkali metal porphyrins were obtained
only recently by Arnold [14]. The graph L [7] implied that
two alkali metal ions might be bound to pairs of adjacent
pyrrole N-atoms, as found with the protons of metal-free
porphyrins. In the presence of tetrahydrofuran (thf),
however, Li2(oep) exists as [Li(thf)4][Li(oep)], type L',
in which only one Li ion sits in the centre of the porphyrin
hole; this anion is a monometallic porphyrin. Na2(oep)(thf)4
and K2(oep)(py)4 exist as isolated molecules in the crystals
and are indeed bimetallic porphyrins of a symmetrical type
L@. The larger alkali ions occupy apical positions of a square
bipyramid reminiscent of a single pyramidal M(p) moiety in
G or K; the four N-atoms form the equatorial square.
Reactions of [Li(thf)4][Li(oep)] with chlorides of the
early transition metals greatly improved the preparations of
porphyrin complexes of this class of metals [15]. In
dilithium phthalocyaninate, Li2(pc), one Li ion is easily
replaced by tetraalkylammonium ions; the other remains
firmly bound and is retained after oxidation of the (pc)2
ligand under formation of the p-radical Li(pc.) [16].
Johann Walter Buchler. Born 1935 in Braunschweig, Germany. Student of Chemistry at Munich
University 195564; Dr, rer. nat. in Inorganic Chemistry 1963. Research Associate in Organic
Chemistry, Technische Universitat Braunschweig (196469) and in Inorganic Chemistry,
Technische Hochschule Aachen (196973). Professor of Inorganic Chemistry at Technische
Hochschule Aachen (197379) and Darmstadt University of Technology (since 1979). Visiting
Professor: Technische Universitat Munchen (1976 and 1977); Universite Louis Pasteur, Strasbourg
(France; 198384); Universite de Bourgogne, Dijon (France; 1992).
Copyright # 2000 John Wiley & Sons, Ltd.
Acknowledgements
Financial support by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie for the projects of
the author is gratefully acknowledged.