Hydrogen-bonded chain structure of a six-coordinate 5,10,15,20-tetraphenylporphinatomanganese(III) complex

doi:10.1016/S0020-1693(00)00360-1

Inorganica Chimica Acta

Volume 315, Issue 1, 16 April 2001, Pages 107-111

https://doi.org/10.1016/S0020-1693(00)00360-1 Get rights and content

Abstract

In methanolic solutions, disproportionation of the TCNQ anion radical to neutral TCNQ⁰ and the dianion TCNQ²⁻ followed by aerobic oxidation of TCNQ²⁻ results in the formation of methyl-4-dicyanomethylene benzoate anion (MDCB⁻). This anion coordinates to the manganese(III) atom of 5,10,15,20-tetraphenylporphinatomanganese(III) leading to the complex whose X-ray crystal structure is reported. The crystal had the monoclinic space group P2₁/n with unit cell dimensions a=13.327(3), b=20.236(6), c=16.914(5) Å and β=92.26(2)°. An important driving force behind the crystal packing is a hydrogen bonding interaction between non-identical ligands of adjacent molecules.

Introduction

Manganese porphyrin complexes are of great importance because of their potential magnetic [1] and catalytic properties [2], [3] whilst salts of the TCNQ anion radical are usually considered because of their low electrical resistivities [4] (although magnetic studies of some of these materials have been undertaken [5], [6]). Previously, several manganese–organic radical complexes have been synthesized and their crystal structures and magnetic properties determined [7], [8], [9]. In particular, oxidation of tetraphenylporphinatomanganese(II) by tetracyanoethylene yields complexes having polymeric chain-like structures and long range magnetic order at depressed temperatures [10], [11]. Additionally, stereochemistry of metalloporphyrins has been studied extensively, not least because of its importance in the reactivity of hemoproteins [12], [13], [14]. Many complexes have been prepared in order to understand the influence that axial ligands have on the physical shape of the porphyrin macrocycle and, more crucially, the effect these ligands have on the electronic structure of the metal atom (i.e. low spin or high spin) [15]. Furthermore, recent studies have revealed the crystal structures of substituted TPPMn complexes with TCNQ anion [16], [17]. In this work, we describe the synthesis and crystal structure of a six-coordinate tetraphenylporphinatomanganese(III) complex of methyl 4-(dicyano methylene) benzoate.

Section snippets

Synthesis

Tetraphenylporphyrin (TPP) was purchased from Aldrich and the chloromanganese(III) complex was prepared by an ordinary method. TPP (1 g, 1.62 mmol) and manganese(II) chloride tetrahydrate (650 mg, 3.3 mmol) were dissolved in dry N,N-dimethylformamide (50 ml) and the solution stirred at 100°C for 3 h. The course of the reaction was monitored by TLC (CH₂Cl₂–silica gel). Following completion of the reaction the solvent was removed under reduced pressure. Chromatographic purification using a silica

Results and discussion

Scheme 1 briefly illustrates the reaction of TPPMnCl (1) [18] (whose crystal structure is already known [19]) with Li⁺[TCNQ radical dot ⁻] (giving 2) [20]² and the subsequent crystallization of

Acknowledgements

The authors would like to thank the Agency of Industrial Science and Technology, Ministry of International Trade and Industry for the financial support under the research project ‘Harmonized Molecular Materials’. J.P.H. and J.S. acknowledge the Science and Technology Agency (STA) for providing STA fellowship.

References (31)

I. Tabushi et al.
Tetrahedron Lett.
(1979)
D. Jérome et al.
Solid State Commun.
(1977)
A.D. Adler et al.
J. Inorg. Nucl. Chem.
(1970)
O. Kahn
Molecular Magnetism
(1995)
J.T. Groves et al.
J. Am. Chem. Soc.
(1988)
J. Ferraris et al.
J. Am. Chem. Soc.
(1973)
J.S. Miller et al.
Acc. Chem. Res.
(1988)
K. Fegy et al.
Angew. Chem., Int. Ed. Engl.
(1998)
A. Caneschi et al.
Inorg. Chem.
(1989)
A. Caneschi et al.
Inorg. Chem.
(1988)

A.J. Epstein et al.

Mol. Cryst. Liq. Cryst.

(1997)

K.-I. Sugiura et al.

Chem. Eur. J.

(1997)

M.F. Perutz

Nature (London)

(1970)

J.L. Hoard

Science

(1971)

J.P. Collman et al.

O₂ binding to heme proteins and their synthetic analogues

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NoteHydrogen-bonded chain structure of a six-coordinate 5,10,15,20-tetraphenylporphinatomanganese(III) complex

Abstract

Introduction

Section snippets

Synthesis

Results and discussion

Acknowledgements

Tetrahedron Lett.

Solid State Commun.

J. Inorg. Nucl. Chem.

Molecular Magnetism

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Acc. Chem. Res.

Angew. Chem., Int. Ed. Engl.

Inorg. Chem.