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Journal of Porphyrins and Phthalocyanines

J. Porphyrins Phthalocyanines 4, 337339 (2000)

Overview

Coordination chemistry of metal tetrapyrrole complexes


unusual geometries and stoichiometries
JOHANN W. BUCHLER*
Institut fur Anorganische Chemie, Darmstadt University of Technology, Petersenstrae 18, D-64287 Darmstadt, Germany
Accepted 17 November 1999
ABSTRACT: Sets of metal tetrapyrrole complexes are presented in which unusual geometries and/or stoichiometries
occur as compared with the usual distorted octahedral structures and molar 1:1 ratio of metal and tetrapyrrole ligand
normally found in metal complexes of porphyrins, phthalocyanines or other tetrapyrrole ligands (hydroporphyrins,
corroles, etc.). Copyright # 2000 John Wiley & Sons, Ltd.
KEYWORDS: metal phthalolyanines; metal porphyrins; metal hexahydroporphyrin derivatives; nonmetal
porphyrins; unusual geometries; unusual stoichiometries

INTRODUCTION; MONOMETALLIC
PORPHYRINS

UNUSUAL GEOMETRIES; SEMIMETALLIC


PORPHYRINS

The coordination chemistry of tetrapyrrole complexes


comprises all chemical reactions in which a tetrapyrrole
system acts as a ligand to a metal or non-metal. The periodic
table of elements forming such complexes comprises all
metals except Be, the semimetals B, Si and As and the nonmetal P; complexes of the chalcogens and halogens are
unknown so far [1]. The class of tetrapyrrole ligands
encompasses the porphyrins and their dihydro, tetrahydro
and hexahydro derivatives, the porphyrin isomers such as
porphycenes, the corrins, the corroles and, last but not least,
the phthalocyanines; from the beginning of the exploration
of these natural or synthetic dyes or pigments it was clear
that their metal complexes were very important [25].
Those porphyrinato or phthalocyaninato complexes
bearing biological or commercial significance are almost
all derived from the square planar, square pyramidal or
distorted octahedral coordination types A, B or C; the socalled bar graphs represent some kind of projection (side
view) of any tetrapyrrole ligand; the two bars indicate the
projections of two opposite pyrrole rings. Type A, M(p) [6],
like a cartoon, just displays the coordination group of a
planar metal(II) porphyrinate 1, and so forth for B and C. A
C show a molar M/(p) ratio = 1:1 and are thus monometallic
porphyrins (or, generally, monometallic tetrapyrroles).

The elements which have been combined with tetrapyrrole


ligands have diverse requirements as to charge and radius of
the respective ion if an accommodation of the latter with the
tetrapyrrole ligands is envisioned. These ligands usually
carry two negative charges and are flat macrocycles with a
central hole formed by four nitrogen donor sites. Their
electron pairs are pointing inwards of the central hole. Thus,
without severe distortion, a porphyrinato ligand would not
be able to accommodate a large central ion such as Pb(II) or
Th(IV). While an Sn(IV) ion in a porphyrin can adopt
octahedral geometry C, as in Sn(OAc)2(tpp) (L = (OAc)),
this is impossible for Zr(IV), Hf(IV), U(IV) or Th(IV).
Therefore octacoordinate species such as G or K, or similar
types for heptacoordination (not shown here), are encountered. The letters marking these and the following
coordination types are the same as those used in an earlier
article on Static coordination chemistry of metalloporphyrins [7] in order to estimate the progress made in the last 25
years.

*Correspondence to: J. W. Buchler, Institut fur Anorganische Chemie,


Darmstadt University of Technology, Petersenstrae 18, D-64287
Darmstadt, Germany.
E-mail: dg7m@hrzpub.tu-darmstadt.de
Copyright # 2000 John Wiley & Sons, Ltd.

Favourable octacoordination of the hard acid metal ion


is achieved in G by ligating two bidentate axial oxygen
ligands such as acetate [8, 9], and in K by double-decker
(sandwich) formation. G represents an unusual geometry
(with normal 1:1 stoichiometry), and K both unusual
geometry and unusual stoichiometry. The double-deckers
M(p)2 account for a molar M/(p) ratio = 1/2 = 0.5 and were
therefore termed semimetallic porphyrins [7]. Particularly
double-deckers have found great attention [10]. The
phthalocyanine counterparts M(pc)2 have interesting electrochromic properties, while the porphyrin counterparts

338

J. W. BUCHLER

M(p)2 show some analogies to the special pair of


bacteriochlorophyll molecules in the photosynthetic apparatus. These are so-called homoleptic double-deckers. The
heteroleptic counterparts [11] bearing one porphyrinato and
one phthalocyaninato ligand, M(p)(pc), allow a chemical
and physical comparison of the respective ligands in one
and the same molecule. Elegant syntheses of well-defined
samples of crystallographically secured phthalocyanine
double- and triple-deckers were described by Homborg
and co-workers [12] and Janczak and Kubiak [13]. see e.g.
Ce(pc)2 [12] or In2(pc)3 [13].

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].

Boron compounds of the postulated type P were already


mentioned [7], later revisited and given a highlight article

[17]; in fact, for B2OF2(tClp) an asymmetric coordination


group as shown in P' was revealed.

BI- AND TETRAMETALLIC


TETRAPYRROLES DERIVED FROM
HEXAHYDROPORHYRINS
A 5,5,10,10,15,15,20,20-octaethyl derivative of hexahydroporphyrin, H4(oehhp) 2, has four protons at the four nitrogen
atoms. The protons could be replaced by alkali metals. Thus
the postulated type T [7] could apply for these compounds.
However, the tetrahedral carbon atoms connecting the
pyrrole rings allow large deviations of the planes of the
pyrrole rings from the mean plane of all core atoms. In fact,
in these hexahydroporphyrins the pyrrole rings are twisted
pairwise away from the imaginable mean plane of the
macrocycle as shown in the bar graph T'. Here the pairs of
black or hatched bars symbolize projections of pyrrole rings
pointing with their pyrrole N-atoms towards or away from
the viewer respectively.

In a series of brilliant papers. Floriani and Floriani-Moro


have prepared metal complexes of 2 [18], e.g.

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.

J. Porphyrins Phthalocyanines 4, 337339 (2000)

METAL TETRAPYRROLE COMPLEXES 339

Li4(oehhp)(thf)3 [19]. In fact, the tetralithium compound has


an irregular structure with a quasi-central lithium ion, three
pyrrole rings severely tilted away from any common plane,
and three lithium ions that maintain, owing to the folded
structure of the tetrapyrrole system, one -type Z1-bond to
the N-atom of a certain pyrrole ring and a p-type Z2-bond to
an NCa or CaCb bond of an adjacent pyrrole ring. This is
schematically shown in bar graph T@.
A flourishing, novel chemistry was derived from
Li4(oehhp). All sorts of transition metals have been
combined with the tetrapyrrole system of 2, and oxidation
reactions and rearrangement processes observed which have
produced, inter alia, porphodimethene complexes [20]. The
reaction of metallic calcium with H4(oehhp) gives a
bimetallic tetrapyrrole Ca2(oehhp)(thf)4 with remarkable
Z3- and Z1-like bonding frames to CNC parts and N-atoms of
alternating pyrrole rings [21] as suggested by the cartoon
T@'. The two calcium ions sit on the main axis of the barrellike structure adopted likewise by the tetraanion of 2 also
sketched as T'.

Acknowledgements
Financial support by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie for the projects of
the author is gratefully acknowledged.

REFERENCES AND NOTES


1. Buchler JW. in The Porphyrins, vol. 1. Dolphin D.(ed.).
Academic Press: New York, 1978; 389.
2. Fischer H, Orth H. Die Chemie des Pyrrols, vol. II, part 1.
Akademie Verlag: Leipzig, 1937.
3. Fischer H, Stern A. Die Chemie des Pyrrols, vol. II, part 2.
Akademie Verlag: Leipzig, 1940.
4. Barrett PA, Dent CE, Linstead RP. J. Chem. Soc. 1936;
1719.
5. Falk JE. Porphyrins and Metalloporphyrins. Elsevier:
Amsterdam, 1964.

Copyright # 2000 John Wiley & Sons, Ltd.

6. Abbreviations used: (p)2, (pc)2, (oep)2 and (tClp)2,


dianions of unsubstituted porphine, phthalocyanine,
2,3,7,8,12,13,17,18-octaethylporphyrin and 5,10,15,20-tetrakis(p-chlorophenyl)porphyrin, respectively; (OAc),
acetate; thf, tetrahydrofuran; py, pyridine; R, alkyl.
7. Buchler JW. In Porphyrins and Metalloporphyrins. Smith
KM.(ed.). Elsevier: Amsterdam, 1975; 157.
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J. Porphyrins Phthalocyanines 4, 337339 (2000)