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Metal Complexes with Tetrapyrrole Ligands, LVIII. Zirconium(IV) and Hafnium(IV) Bisporphyrinate Double Deckers: Synthesis, Spectra, Redox Potentials, and Structure (1991)

Buchler, Johann W. ; Cian, André De ; Fischer, Jean ; [et al.]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1051-1058

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ISSN: 0009-2940

Keywords: Zirconium porphyrins ; Hafnium porphyrins ; Porphyrin double deckers ; Metal bisporphyrinates ; Chemistry ; Inorganic Chemistry

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Notes: The synthesis of new zirconium and hafnium bisporphyrinate double deckers M(P)2 (M=Zr, Hf; P=OEP, TPP)2,3) is described. The complexes are characterized by UV/Vis/NIR and 1H-NMR spectroscopy and cyclic voltammetry. As compared with M=Ce, the redox potentials or the energies of the nearinfrared absorption bands of the corresponding radical cations [M(P)2]+ are lower by ≍ 0.2 V or higher by ≍ 2000 cm-1, respectively, Hence, there is a stronger π-π interaction between the porphyrin ligands as compared with the cerium analogues due to the smaller ionic radii of Zr(IV) and Hf(IV). X-ray crystallography of Zr(TPP)2 confirms the sandwich-like structure of the compound and the close proximity of the porphyrin ligands.

Additional Material: 4 Ill.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1002/cber.19911240511

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Metal Complexes with Tetrapyrrole Ligands, LXI. Structure and Products of Electrochemical Oxidation of Zirconium(IV) and Hafnium(IV) Bisporphyrinate Double-Deckers (1992)

Buchler, Johann W. ; De Cian, André ; Elschner, Steffen ; [et al.]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 107-115

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ISSN: 0009-2940

Keywords: Zirconium porphyrins ; Hafnium porphyrins ; Porphyrin double-deckers ; Metal bisporphyrinates ; Chemistry ; Inorganic Chemistry

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Notes: The electrochemical oxidation of zirconium and hafnium double-deckers M(P)2 (M=Zr, Hf; P=OEP, TPP) (Scheme 1)2) leads to mono- and dications which show near infrared absorption bands which are of ≈ 2000 cm-1 higher energy than those of the corresponding cerium double-decker cations. [Zr(OEP)2]X, [Zr(OEP)2]X2, and [Zr(TPP)2]X (X=ClO4- and PF6-) are isolated after electrochemical oxidation and are characterized by IR and NMR spectroscopy. Magnetic susceptibility measurements (2 K 〈 T 〈 300 K) of the solids confirm the strong coupling of the electron spins in the diamagnetic dication salt [Zr(OEP)2][ClO4]2. The molecular structure of Zr(OEP)2 is elucidated by an X-ray structural analysis.

Additional Material: 5 Ill.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1002/cber.19921250118

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Metal complexes with tetrapyrrole ligands, LVII. Synthesis, spectra, and structure of nitridorhenium(V) porphyrins (1990)

Buchler, Johann W. ; Cian, André De ; Fischer, Jean ; [et al.]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2247-2253

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ISSN: 0009-2940

Keywords: Rhenium(V) porphyrins ; Nitridorhenium(V) complexes ; Rhenium-Nitrogen triple bonds ; Metalloporphyrins ; Chemistry ; Inorganic Chemistry

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Notes: Oxorhenium(V) porphyrins ReO(P)X (X = Cl, Br) or [ReO(P)]2O, or trichlororhenium(V) porphyrins ReCl3(P) (P = OEP, TPP, TTP, TAP, TCIP, TMP)2,3, respectively, are transformed into nitridorhenium(V) porphyrins ReN(P) with hydrazine hydrate in the presence of ethanol, in good yields. The diamagnetic complexes are stable towards hydrolysis and contain pentacoordinate ReV in a square pyramid of nitrogen donor atoms. Their structure is deduced spectrometrically and is proven in the case of ReN(OEP) by X-ray crystallography. The UV/Vis- and 1H-NMR spectra of the new nitrido complexes are compared with those of the corresponding zinc(II) porphyrins.

Additional Material: 3 Ill.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1002/cber.19901231204

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