Synthesis and magnetic resonance spectroscopy of novel phenolato-bridged manganese(III) and iron(III)-manganese(III) porphyrin complexes

Godziela, Gregory M.; Tilotta, David C.; Goff, Harold M.

doi:10.1021/ic00233a009

Cited by 26 publications

(15 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Numerous structures ranging from discrete noncyclic arrays 1-13 to polymers, 14-25 and from cyclic oligomers [26][27][28][29][30][31][32][33] to dendrimers, 34,35 have been assembled using axial ligand coordination to metalloporphyrins. Reports of structures consisting * To whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Rh(III) Porphyrins as Building Blocks for Porphyrin Coordination Arrays: From Dimers to Heterometallic Undecamers

et al. 2001

View full text Add to dashboard Cite

The coordination chemistry of a Rh(III) porphyrin building block was investigated with a view to the construction of heterometallic arrays of porphyrins. The Rh(III) porphyrin was found to coordinate methanol in the solid state and weakly in CDCl(3) solution. Crystallization afforded five coordinate pi stacked Rh(III) porphyrins. The distribution of products from reaction of Rh(III) porphyrin with DABCO, 4,4'-bipyridine, and 4,4'-bipyrimidine could be displaced toward dimeric species by silica gel column chromatography or recrystallization which served to remove excess ligand. Weak coordination to nitriles was observed, although it was sufficiently strong to organize a dimeric complex of 5,5'-dicyano-2,2'-bipyridine in the solid state. Complexes with 4,4'-bipyrimidine and 5,5'-dicyano-2,2'-bipyridine possess uncoordinated chelating nitrogen atoms. Larger heterometallic porphyrin arrays were assembled using a combination of Sn(IV) and Rh(III) porphyrin coordination chemistry. A Sn(IV) porphyrin acted as a core around which were coordinated two isonicotinate groups, carboxylic acid functionalized porphyrins, or porphyrin trimer dendrons. Rh(III) porphyrins were coordinated to pyridyl groups at the periphery of these entities. In this way an eleven porphyrin array, with four different porphyrin metalation states, was assembled. The diamagnetic nature of both the Rh(III) and Sn(IV) porphyrins, the slow ligand exchange kinetics on the NMR time scale, and tight ligand binding permitted the porphyrin arrays to be analyzed by two-dimensional (1)H NMR techniques.

show abstract

Section: Introductionmentioning

confidence: 99%

Rh(III) Porphyrins as Building Blocks for Porphyrin Coordination Arrays: From Dimers to Heterometallic Undecamers

et al. 2001

View full text Add to dashboard Cite

show abstract

“…[4Ϫ7] Insertion of an iron ion into 5-(2-hydroxyphenyl)-10,15,20-tritolylporphyrin (TTOPH 2 ) or 5-hydroxy- The structure of [(TTOP)Fe III ] 2 was determined by X-ray crystallography and the retention of the dimeric structure in solution was demonstrated by 1 H NMR spectroscopy. [8,9] Goff et al characterized the manganese(III) dimer [(TTOP)Mn III ] 2 and detected, by means of 1 H NMR spectroscopy, the diphenoxo-bridged heteronuclear complex [(TTOP)Fe III (TTOP)Mn III ]. [9] (Oxophlorin)iron complexes are significant in the context of their involvement as intermediates in the conversion of (porphyrin)iron to biliverdin in the oxidative heme destruction.…”

Section: Introductionmentioning

confidence: 99%

“…[8,9] Goff et al characterized the manganese(III) dimer [(TTOP)Mn III ] 2 and detected, by means of 1 H NMR spectroscopy, the diphenoxo-bridged heteronuclear complex [(TTOP)Fe III (TTOP)Mn III ]. [9] (Oxophlorin)iron complexes are significant in the context of their involvement as intermediates in the conversion of (porphyrin)iron to biliverdin in the oxidative heme destruction. [11,12] Masuoka and Itano characterized the (oxophlorin)iron(III) dimer [(OEPO)Fe III ] 2 by a range of spectroscopic techniques.…”

Section: Introductionmentioning

confidence: 99%

“…[31,32] The hyperfine shift patterns are particularly sensitive to the ligation, oxidation and spin state of the metal ion. For instance, the (porphyrin)iron(III) complexes bridged by ligands containing one or more oxygen atoms present 1 H NMR spectroscopic patterns unequivocally explainable in terms of their dimeric [8,9,13] or trimeric [16Ϫ19] structures. In this contribution our investigations have been focused on (5-hydroxy-10,15,20-triphenylporphyrin)-and (5-oxo-10,15,20-triphenylphlorin)iron(III) complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Monomeric and Dimeric Iron(III) Complexes of 5‐Hydroxy‐10,15,20‐triphenylporphyrin: Formation of Cyano and Pyridine Complexes of (5‐Oxo‐10,15,20‐triphenylphlorin)iron

Wojaczyński

Stępień

Latos‐Grażyński

2002

Euro J of Inorganic Chem

View full text Add to dashboard Cite

The reaction of [(TrPP)FeII(py)2] (TrPP = dianion of 5,10,15‐triphenylporphyrin) with hydrogen peroxide results in oxygenation of the (porphyrin)iron and the formation of (10,15,20‐triphenyl‐5‐oxophlorin)iron [(5‐O‐TrPP)Fe(py)2]. Coupled oxidation of [(TrPP)FeIIICl] in the presence of ascorbic acid and potassium cyanide in methanol leads to oxidative hydroxylation of the porphyrin ring to form a cyclic dimer [(5‐O‐TrPP)FeIII]2. Three out of four pyrrole 1H NMR resonances of the dimeric complex present the characteristic displacement with respect to the typical position for the high‐spin (tetraphenylporphyrin)iron(III) complexes. The linewidths of the β‐H pyrrole resonances correlate with specific locations of the respective protons within the dimeric structure. Addition of HCl to [(5‐O‐TrPP)FeIII]2 results in cleavage of the dimer producing [(5‐OH‐TrPP)FeIIICl]. [(5‐O‐TrPP)FeIII]2 is also split with acetic anhydride to give (5‐acetoxy‐10,15,20‐triphenylporphyrin)iron(III). In the presence of [D5]pyridine or a large excess of cyanide ion, [(5‐O‐TrPP)FeIII]2 undergoes cleavage to form air‐sensitive [(5‐O‐TrPP)Fe(py)2] or [(5‐O‐TrPP)Fe(CN)2]2−. The pyrrole pattern observed for [(5‐O‐TrPP)Fe(py)2] is similar to that determined on the basis of an analysis carried out for four (oxophlorin)iron regioisomers obtained from hemes. For comparison, the characteristic 1H NMR features of the typical (5‐substituted‐10,15,20‐triphenylporphyrin)iron(III) complexes have been investigated for the series of high‐spin and low‐spin complexes. The spin‐density distribution in the (oxophlorin)iron skeleton is dominated by the radical‐like electronic structure. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

show abstract

“…Oxygen atom donors are also useful for generating supramolecular metalloporphyrin systems but these associates are obviously less stable and more difficult to investigate in comparison to those formed through metal-nitrogen coordinative bonding. [20][21][22][23][24][25][26] However, these supramolecular tetrapyrrole systems which are known to be generated through weak intermolecular interactions. 7,[27][28][29] For some time, different research groups have focused on chemical modeling of the photosynthesis machinery using synthetic tetrapyrroles containing oxygen donor sites.…”

mentioning

confidence: 99%

Coordination self-assembly through weak interactions in meso-dialkoxyphosphoryl-substituted zinc porphyrinates

et al. 2019

View full text Add to dashboard Cite

show abstract

Synthesis and magnetic resonance spectroscopy of novel phenolato-bridged manganese(III) and iron(III)-manganese(III) porphyrin complexes

Cited by 26 publications

References 0 publications

Rh(III) Porphyrins as Building Blocks for Porphyrin Coordination Arrays: From Dimers to Heterometallic Undecamers

Rh(III) Porphyrins as Building Blocks for Porphyrin Coordination Arrays: From Dimers to Heterometallic Undecamers

Monomeric and Dimeric Iron(III) Complexes of 5‐Hydroxy‐10,15,20‐triphenylporphyrin: Formation of Cyano and Pyridine Complexes of (5‐Oxo‐10,15,20‐triphenylphlorin)iron

Coordination self-assembly through weak interactions in meso-dialkoxyphosphoryl-substituted zinc porphyrinates

Contact Info

Product

Resources

About