Synthesis of rhenium(II) porphyrin complexes and crystal structure of bis(trimethylphosphine)(tetra-p-tolylporphyrinato)rhenium(II)-toluene

Collman, James P.; Garner, James M.; Kim, Kimoon; Ibers, James A.

doi:10.1021/ic00297a037

Cited by 15 publications

(3 citation statements)

References 7 publications

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“…To overcome these, we report a one-pot strategy to synthesize metalloporphyrins in very good yield. Such a reaction was carried out in an organic melt like benzoic acid as the matrix in a solid-state reaction (Scheme ) . Heating a mixture of 5,10,15,20- meso -tetraphenylporphyrin (H 2 TPP) and an equivalent amount of [M(NO) 2 py 2 Cl 2 ] (M = Mo, W) in a benzoic acid melt affords the formation of metalloporphyrins in quantitative yield.…”

Section: Introductionmentioning

confidence: 99%

Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate

Nandi¹,

Sarkar²

2012

Inorg. Chem.

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A new route is developed for the synthesis of molybdenum and tungsten porphyrins using [M(NO)(2)py(2)Cl(2)] (M = Mo, W) as the metal source and TPP (dianion of 5,10,15,20-meso-tetraphenylporphyrin) in the benzoic acid melt. Complexes [Mo(V)O(TPP)(OOCPh)] (1) and [W(V)O(TPP)(OOCPh)] (2) are isolated in almost quantitative yield. These are characterized by single-crystal X-ray structure analysis, electron paramagnetic resonance, electronic and IR spectroscopy, and magnetic moment measurements. Benzenethiol substitutes for PhCOO(-) in 1, forming an intermediate thiolato complex that responds to the intramolecular redox reaction across the Mo(V)-SPh bond to yield [Mo(IV)O(TPP)] (3). Under an excess of benzenethiol, PhS(-) is coordinated to the vacant site in 3, which under aerial oxidation is oxidized to benzenesulfonate to form [Mo(V)O(TPP)(O(3)SPh)] (4). 2 undergoes similar aerial oxidation chemistry albeit slowly.

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Section: Introductionmentioning

confidence: 99%

Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate

Nandi¹,

Sarkar²

2012

Inorg. Chem.

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“…Pentavalent rhenium oxo and rhenium nitrido porphyrins have also been known for decades. The next major developments came in the 1980s in the form of monomeric rhenium(II) porphyrins and metal–metal triple-bonded rhenium(II) porphyrin dimers. , Rhenium corroles are of more recent provenance: although one was serendipitously isolated some time ago, a general synthetic route to Re V O corroles (as well as to 99 TcO corroles) emerged only a few years ago . The simplicity of latter route has also allowed for peripheral functionalization of Re V O corroles via electrophilic aromatic substitution reactions such as halogenation and formylation .…”

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confidence: 99%

Rhenium Biscorrole Sandwich Compounds: XAS Evidence for a New Coordination Motif

et al. 2023

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The interaction of three free-base meso-tris(p-X-phenyl)corroles H3[TpXPC] (X = H, CH3, OCH3) with Re2(CO)10 at 235 °C in the presence of K2CO3 in o-dichlorobenzene has led to putative rhenium biscorrole sandwich compounds with the formula ReH[TpXPC]2. Density functional theory calculations and Re L3-edge extended X-ray absorption fine structure measurements suggest a seven-coordinate metal center, with the “extra” hydrogen located on one of the corrole nitrogens. The complexes can be deprotonated by a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene, resulting in a substantial sharpening of the UV–vis spectra and split Soret bands, consistent with the generation of C 2-symmetric anions. Both the seven-coordinate neutral and eight-coordinate anionic forms of the complexes represent a new coordination motif in the field of rhenium–porphyrinoid interactions.

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“…Seine Synthese ist ku È rzlich optimiert worden, und dabei sind auch seine chemischen und spektroskopischen Eigenschaften ausfu È hrlich charakterisiert worden [4,5]. Desweiteren sind inzwischen besser lo È sliche, ringsubstituierte Derivate von [ReNpc 2± ] synthetisiert worden [5,6] [20] befindet sich das Re-Atom in der Ebene der vier Pyrrol-N-Atome (N p : N1, N3) des pc 2± -Liganden und koordiniert in den axialen Positionen zwei P-Atome (P) der Triphenylphosphin-Liganden in trans-Anordnung. Die (Re±N1)-, (Re±N3)-und (Re±P)-Absta È nde betragen 2,011(9) A Ê , 2,003(8) A Ê und 2,516(3) A Ê .…”

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trans-Bis(triphenylphosphin)phthalocyaninato(2-)rhenium(II): Synthese, Eigenschaften und Kristallstruktur

Göldner¹,

Kienast²,

Homborg³

1998

Z. anorg. allg. Chem.

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Synthesis of rhenium(II) porphyrin complexes and crystal structure of bis(trimethylphosphine)(tetra-p-tolylporphyrinato)rhenium(II)-toluene

Cited by 15 publications

References 7 publications

Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate

Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate

Rhenium Biscorrole Sandwich Compounds: XAS Evidence for a New Coordination Motif

trans-Bis(triphenylphosphin)phthalocyaninato(2-)rhenium(II): Synthese, Eigenschaften und Kristallstruktur

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