Tetraphenylporphine Complexes Research Articles

High-performance thin-layer chromatography of rare earth tetraphenylporphine complexes

The thin-layer chromatographic (TLC) behaviour of the metal complexes of tetraphenylporphine with twelve rare earths, viz., Y(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III) and Lu(III), on TLC plates coated with octadecylsilica gel (C 18) and aminopropylsilica gel (NH 2) is described. Most of these metal complexes can be successfully developed without undesirable demetallation of the complexes in the migration process with a methanol-water mixture (90:10, v/v) containing both acetylacetone and diethylamine, typically at 5—10% and 0.5—1% for the C 18 and NH 2 plates, respectively. On a C 18 plate, the mobility ( R F) of the complexes of lanthanide metals tends to decrease in the order of the atomic numbers of the metals, whereas on an NH 2 plate the reverse order occurs. On both C 18 and NH 2 plates the R F value of the Y(III) complex lies between those of the Dy(III) and Ho(III) complexes.

The free base of tetraphenylporphine serves as a host for alkali metal salts

The unionized form of tetraphenylporphine complexes alkali metal salts in acetone with association constants ranging from 6.0 to 60 M −1.

Multiphoton ionization of transition-metal tetraphenylporphines. Metal complexes which display molecular ionization

The tetraphenylporphine (TPP) complexes of cobalt, nickel, and copper were studied by multiphoton ionization mass spectrometry. These complexes were found to exhibit molecular ionization without ligand predissociation using radiation at 266 nm. The laser power dependences for Cu(TPP) + and Cu + ion formation show that Cu(TPP) + is not formed by an ion/molecule reaction with Cu +. The ionization behavior of these complexes is discussed in terms of a gas-phase macrocyclic ligand effect which inhibits efficient molecular dissociation prior to ionization.

Back-bonding in ruthenium porphyrins as monitored by resonance Raman spectroscopy

Resonance Raman spectra are reported for Ru/sup II/ complexes of octaethylporphyrin (OEP) and tetraphenylporphine (TPP) with pyridine, methanol, and CO axial ligands, using both B- and Q-band excitation. For Ru/sup II/ OEP(CO)(MeOH) the porphyrin skeletal mode frequencies above 1370 cm/sup -1/ agree remarkably well with the values calculated on the basis of the porphyrin core size by using parameters derived earlier for iron protoporphyrin complexes. These frequencies shift both positively and negatively when the CO is replaced by pyridine due to ..pi..-back-donation from Ru to the porphyrin ..pi.. orbitals. The shift pattern is the same as that observed for the bis(imidazole) adduct of iron(II) protoporphyrin, relative to the core size predictions, and the extent of the shifts is very similar in the two cases. Thus, ..pi..-back-bonding to the porphyrin appears to be quantitatively similar for Ru/sup II/ and Fe/sup II/. ..pi..-Back-bonding shifts are also reported for Ru/sup II/TPP(py)/sub 2/. For Ru/sup II/OEP(CO)(py) the Ru-CO stretching, Ru-C-O bending, and C-O stretching modes are observed at 513, 578, and 1930 cm/sup -1/. For Fe/sup II/ porphyrins, the M-CO and C-O frequencies are somewhat lower and higher, respectively, implying greater back-donation to the bound CO for Ru/sup II/ than for Fe/sup II/.

Specific retention behaviour of metal (III) tetraphenylporphyrins in non-aqueous, reversed high-performance liquid chromatography

The Co(II), Ni(II), Fe(III) and V(IV) complexes of tetraphenylporphine (TPP) can be eluted at short retention times from a LiChrosorb RP-18 column with pure ethanol. However, both Mn(III) and Co(III) complexes of metal TPP chloride type are so strongly retained on the column that they cannot be eluted. While the retention of other metal teraphenylporphine complexes was not affected, that of the metal(III) complexes of the TPP chloride type especially MnTPPCl and CoTPPCl, decreases dramatically with an increase in the concentration of NH4Cl added into the mobile phase; a linear relationship between logk' and log[NH4Cl], with the slope of about−1, has been observed for these two metal(III) complexes in the NH4Cl concentration range from 2.5×10−4 to 1.3×10−2 mol/l. Thus, the specific control of the retention of the metal(III) complexes is enabled by conditioning the NH4Cl content of the mobile phase, and the chromatographic separation is demonstrated.

Surface-enhanced resonance Raman scattering of trivalent metal tetraphenylporphine complexes in a layered structure of a CaF 2-roughened substrate/sample/Ag

Surface-enhanced resonance Raman scattering spectra were measured for trivalent metal tetraphenylporphine complexes, such as Fe(III)TPPCl, Mn(III)TPPCl and Cr(III)TPPCl, in a layered structure having a CaF 2-roughened substrate/sample/Ag configuration. Each surface spectrum is appreciably different from the resonance Raman scattering spectrum of the corresponding metalloporthine but similar to the RRS spectrum of the corresponding μ-oxo dimer ([Fe(III)TPP] 2O or [Mn(III)TPP] 2) or a monohydroxy complex Cr(III)TPPOH. This result indicates that, when the above-mentioned metalloporphines interact with Ag vapor during its deposition process, the complexes are converted to the μ-oxo dimers and the monohydroxy complex, respectively.

Surface-enhanced resonance raman scattering of trivalent metal tetraphenylporphine complexes in a layered structure of a CaF 2-roughened substrate/sample/Ag

Abstract Surface-enhanced resonance Raman scattering spectra were measured for trivalent metal tetraphenylporphine complexes, such as Fe(III)TPPCl, Mn(III)TPPCl and Cr(III)TPPCl, in a layered structure having a CaF 2 -roughened substrate/sample/Ag configuration. Each surface spectrum is appreciably different from the resonance Raman scattering spectrum of the corresponding metalloporthine but similar to the RRS spectrum of the corresponding μ-oxo dimer ([Fe(III)TPP] 2 O or [Mn(III)TPP] 2 ) or a monohydroxy complex Cr(III)TPPOH. This result indicates that, when the above-mentioned metalloporphines interact with Ag vapor during its deposition process, the complexes are converted to the μ-oxo dimers and the monohydroxy complex, respectively.

Structure sensitive bands in the vibrational spectra of metal complexes of tetraphenylporphine

The i.r. and RR spectra of twenty Fe(TPP)LL′ type complexes have been measured to locate structure-sensitive bands. In i.r. spectra, band I (1350-1330 cm −1) and band III (469-432 cm −1) are spin-state sensitive whereas band II (806-790 cm −1) is oxidation-state sensitive and slightly spin-state sensitive in the Fe(II) state. To examine the nature of these bands, the i.r. spectra of Co(TPP), (Fe(TPP)) 2O and their d 8 and d 20 analogs have been measured, and empirical assignments proposed. In RR spectra, band C (1545-1498 cm −1, ap) and band D (1565-1540 cm −1, p) are spin-state sensitive whereas band E (391-376 cm −1, p) is sensitive to both spin and oxidation states. These results on RR spectra are in good agreement with those of previous workers.

NEW OXOMOLYBDENUM(V) COMPLEXES OF TETRAPHENYLPORPHINE WITH UNIVALENT LIGANDS

Abstract New tetraphenylporphine complexes of oxomolybdenum(V), MoO(tpp)X(X = NCS and Br), were synthesized, and characterized by means of IR, ESR, and electronic spectra. The formation of a hyperoxide complex, MoO(tpp)(O2), in dichloromethane was confirmed.

Nitrogen 1s photoelectron spectra of octaethylporphyrin and tetraphenylporphine complexes of lanthanides

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNitrogen 1s photoelectron spectra of octaethylporphyrin and tetraphenylporphine complexes of lanthanidesKazuyuki Tatsumi and Minoru TsutsuiCite this: J. Am. Chem. Soc. 1980, 102, 2, 882–884Publication Date (Print):January 1, 1980Publication History Published online1 May 2002Published inissue 1 January 1980https://doi.org/10.1021/ja00522a092RIGHTS & PERMISSIONSArticle Views93Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (397 KB) Get e-Alerts Get e-Alerts

PREPARATION AND CHARACTERIZATION OF OXOMOLYBDENUM(V) -PORPHYRIN COMPLEXES

Abstract Oxomolybdenum(V) complexes of tetraphenylporphine and octaethylporphine, Mo(O) (OC2H5) (TPP) and Mo(O) (OEP)X (X = Cl or OCH3), were prepared from the corresponding porphyrins by reaction with molybdenum pentachloride. Both ESR and electronic spectra indicate that the complexes coordinated with an alkoxide group exist in dichloromethane or chloroform as a single monomeric species, while more than one species are present in aromatic solvents for each of the complexes.

UNUSUAL METALLOPORPHYRINS. PHOSPHORUS COMPLEXES OF TETRAPHENYLPORPHINE

Abstract The synthesis and spectral properties of several phosphorus complexes of tetraphenylporphine (TPP) are reported. The compounds appear to have the form (TPP)P(V)X2 +Y− as previously reported by Gouterman et al. for the analogous octaethylporphyrin (OEP) complexes. The electronic and nmr spectra show a striking dependence on the nature of the anionic ligand X, which has not previously been reported and appears to be inconsistent with a symmetrical in-plane structure.

Vibrational spectra of transition metal complexes of tetraphenylporphine

Abstract The far i.r. spectra of tetraphenylporphine complexes of Pd(II), Co(II), Cu(II), Ag(II) and Zn(II) have been obtained. In order to aid in the assignment of the metal-nitrogen vibrations the metal isotope technique has been applied to the Ni, Cu, and Zn complexes. Vibrations containing contributions from the metal-nitrogen stretching coordinate have been assigned based on these metal isotope data and the results of a normal coordinate analysis of Zn(II)-porphine. The variation of the frequencies of the major bands is shown to be dependent upon the number of d electrons and is explained on the basis of ligand field stabilization energy.

Study of the structure of some tetraphenylporphine complexes of cobalt 57 by means of emission gamma resonance spectroscopy

Study of the structure of some tetraphenylporphine complexes of cobalt 57 by means of emission gamma resonance spectroscopy

Preparation of indium (III) tetraphenylporphine complexes

Preparation of indium (III) tetraphenylporphine complexes

Studies on Metastable States of Porphyrins. II. Spectra and Decay Kinetics of Tetraphenylporphine, Zinc Tetraphenylporphine and Bacteriochlorophyll1

The flash technique used earlier to study the metastable states of chlorophyll was applied to tetraphenylporphine, - zinc tetraphenylporphine, and bacteriochlorophyll in toluene and pyridine solution. The spectra all show a main band just below the Soret peak, as well as other regularities. The decay law is again --dC*/dt = k1C* + k2(C*)2 + The respective rate constants for all the compounds are almost the same, except for a much faster first-order decay in bacteriochlorophyll. Finally, little or no flash-bleaching is observed with the Cu2+, Co2+, and Ni2+ complexes of tetraphenylporphine.