Stereochemical Control in Metalloporphyrin Chemistry:  Synthesis and Characterization of cis- and trans-Sn(porphyrin)Ph2

Dawson, Denisha Y.; Sangalang, Joan; Arnold, John

doi:10.1021/ja961007c

Cited by 29 publications

(28 citation statements)

References 15 publications

(22 reference statements)

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“…A large number of tin(IV) porphyrins of the type [(P)SnX 2 ] (P is either tetraaryl or octaethyl porphyrin and X is an 'inorganic' axial ligand such as halide, OH -, ClO 4 -, S 2or Se 2-) [7-10, 15-21, 36-39] and organometallic complexes of the type [(P)Sn(R) 2 ] (R = alkyl/aryl group) [40,41] are well known in the literature. Relatively less well studied are the corresponding porphyrins of the type [(P)Sn(OR) 2 ] where OR is an organic (alkoxy/aryloxy/acidoxo etc.)…”

Section: Resultsmentioning

confidence: 99%

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Reddy

Maiya

2002

J. Porphyrins Phthalocyanines

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Spectroscopic, electrochemical and fluorescence properties of five octahedral tin(IV) porphyrins ([(TpTP)Sn(O-m,p-C 6 H 3 (CH 3 ) 2 ) 2 ] (1), [(TpTP)Sn(O-p-C 6 H 4 (CH 3 )) 2 ] (2), [(TpTP)Sn(O-C 6 H 5 ) 2 ](3), [(TpTP)Sn(O-p-C 6 H 4 O-o,p-C 6 H 3 (NO 2 ) 2 ) 2 ] (4) and [(TpTP)Sn(O-p-C 6 H 4 (NO 2 )) 2 ] (5)) bearing electron donating/electron withdrawing aryloxo subunits as the axial ligands are investigated in detail. These complexes have been synthesized by the reaction of 5,10,15,20-tetra(4-methylphenyl)porphyrinato tin(IV) dihydroxide ([(TpTP)Sn(OH) 2 ]) and either 3, 4-dimethylphenol, p-cresol, phenol, 4-(2,4dinitrophenoxy)phenol or p-nitrophenol and were isolated in good-to-moderate yields. Analysis of the spectral data (FAB mass, IR, UV-vis and 1 H NMR) of 1 -5 suggests that the two trans axial aryloxo ligands are strongly bound in a symmetric manner at the tin center in these complexes. Specifically, the general symmetry observed in the 1 H NMR spectra and the ring current effect experienced by the protons present on the axial ligands are revealing in this regard. Each porphyrin ring undergoes two successive, reversible/quasi-reversible, one-electron reductions in CH 2 Cl 2 , 0.1 M TBAP. The bound nitroaromatic axial ligands of complexes 4 and 5 could also be reduced under the same set of experimental conditions. The wavelengths of maximum emission, the singlet energies and the Stokes' shifts observed in the fluorescence spectra of 1 -5 are close to the corresponding parameters of the reference porphyrin, [(TpTP)Sn(OH) 2 ]. On the other hand, fluorescence intensities of complexes 1 -4 are quenched in comparison with that of [(TpTP)Sn(OH) 2 ] in three different solvents. A detailed analysis of the emission and redox potential data indicates that a photoinduced electron transfer from the axial aromatic subunit to singlet state of the basal tin(IV) porphyrin can, in principle, explain the fluorescence quenching observed in these donor-acceptor systems. The spectroscopic and redox features of these tin(IV) porphyrins are compared with those of the analogous phosphorus(V) porphyrins reported by us earlier.

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Section: Resultsmentioning

confidence: 99%

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Reddy

Maiya

2002

J. Porphyrins Phthalocyanines

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“…There are six derivatives [366,466,571,626,634] where a square plane is created by a tetradentate macrocycle with the axial positions occupied by monodentate C-donor ligands. The structures of two of them are shown in Figures 8 and 9.…”

Section: ιοmentioning

confidence: 99%

Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Monomeric Derivatives

Holloway¹,

Melnı́k²

2000

Main Group Metal Chemistry

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“…[18][19][20][21] Organometallic chemistry of these metal macroheterocycles has been developed mainly for metalloporphyrins due to their solubility in organic solvents that allows one to obtain crystals of indium, gallium and tin porphyrins with alkyl, vinyl, phenyl or phenylacetylenyl substituents at the metal centers. [8][9][10][11][14][15][16][17] Compounds with tin porphyrin (SnP) can contain one and two alkyl or phenyl ligands at the metal center, and can be obtained by oxidative addition of CH 3 I to Sn II P, 10 direct synthesis from Li 2 P and SnCl 2 R 2 , or the interaction of the R 2 Mg and Grignard reagents with Sn IV Cl 2 P. 11 At the same time, only a few such compounds are known for metal phthalocyanines. For example, the structure of phenylindium octakis(hexyl)phthalocyanine can be found in the CCDC database only for metal phthalocyanines with phenyl substituents at the metal atoms.…”

Section: Introductionmentioning

confidence: 99%

SnPhPc phthalocyanines with dianion Pc²⁻ and radical trianion Pc˙³⁻ macrocycles: syntheses, structures, and properties

et al. 2016

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The interaction of Sn(IV)Cl2Pc with an excess of NaBPh4 in the presence of fullerenes C60 and C70 provides complete dissolution of Sn(IV)Cl2Pc and the formation of blue solutions from which the crystals of [SnPhPc(2-)](+)(BPh4)(-)·C6H14 () or [SnPhPc˙(3-)]·C6H4Cl2 () were selectively isolated. According to the optical spectra, salt contains dianionic Pc(2-) macrocycles, whereas macrocycles are reduced to form the Pc˙(3-) radical trianions in . As a result, the phthalocyanine macrocycle is dianionic in , and the positive charge of Sn(IV) is compensated by the Ph(-), Pc(2-), and BPh4(-) anions in this compound. The formally neutral compound contains two anionic species of Ph(-) and Pc˙(3-) and the Sn(IV) ion as the counter cation. Phenyl substituents are linked to the Sn(IV) atoms by the Sn-C(Ph) bonds of 2.098(2) () and 2.105(2) Å () length. The dianionic Pc(2-) macrocycle significantly deviates from planarity in while Pc˙(3-) is planar in . Salt manifests only a weak impurity EPR signal. Compound manifests an intense EPR signal with g = 2.0046 and a linewidth of 0.5 mT at 298 K due to the presence of Pc˙(3-). Spins are weakly antiferromagnetically coupled in the π-stacking [SnPhPc˙(3-)]2 dimers of with a Weiss temperature of -3 K and the estimated magnetic exchange interaction J/kB = -0.23 K.

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Stereochemical Control in Metalloporphyrin Chemistry: Synthesis and Characterization of cis- and trans-Sn(porphyrin)Ph₂

Abstract: In metalloporphyrin chemistry, cis versus trans coordination geometries are generally assumed to be controlled by the nature of the metal ion, with the trans (or axial) arrangement being

Cited by 29 publications

References 15 publications

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Monomeric Derivatives

SnPhPc phthalocyanines with dianion Pc²⁻ and radical trianion Pc˙³⁻ macrocycles: syntheses, structures, and properties

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Stereochemical Control in Metalloporphyrin Chemistry: Synthesis and Characterization of cis- and trans-Sn(porphyrin)Ph2

Abstract: In metalloporphyrin chemistry, cis versus trans coordination geometries are generally assumed to be controlled by the nature of the metal ion, with the trans (or axial) arrangement being

Cited by 29 publications

References 15 publications

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Bis(aryloxo) derivatives of tin(IV) porphyrins: synthesis, spectroscopy and redox activity

Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Monomeric Derivatives

SnPhPc phthalocyanines with dianion Pc2− and radical trianion Pc˙3− macrocycles: syntheses, structures, and properties

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Stereochemical Control in Metalloporphyrin Chemistry: Synthesis and Characterization of cis- and trans-Sn(porphyrin)Ph₂

SnPhPc phthalocyanines with dianion Pc²⁻ and radical trianion Pc˙³⁻ macrocycles: syntheses, structures, and properties