Carbon–sulfur bond cleavage reactions of dibenzothiophene derivatives mediated by iron and ruthenium carbonyls

Hirotsu, Masakazu; Tsuboi, Chiaki; Nishioka, Takanori; Kinoshita, Isamu

doi:10.1039/c0dt00768d

Cited by 30 publications

(43 citation statements)

References 17 publications

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“…The Fe(1)−C(8) bond distances for 1 (1.9456(18) Å) and 2 (1.956(3) Å) are similar to those of diiron complexes derived from PyDBT derivatives or QTs, 33,36,37 and the Fe(1)−C (18) bond trans to C(8) is ca. 0.05 Å longer than the Fe(1)−C (19) bond, indicating the trans influence of the central C donor of the N,C,S-tridentate ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 59%

“…These findings suggest that complex 1 have a C,Sbridged dinuclear structure with the formula [{Fe(μ-qvbtκ 3 N,C,S)(CO) 2 }Fe(CO) 3 ] (Scheme 2), which is similar to that of diiron carbonyl complexes prepared from pyridyl-substituted dibenzothiophene (PyDBT) or quinolyl-substituted thiophenes (QTs). 33,36,37 In the 1 H NMR spectrum of 2, a significant downfield shift was observed for the quinoline CH adjacent to the vinyl group (7.50 ppm for 1, 9.08 ppm for 2), which is due to the C−H•••O(methoxy) short contact (mentioned later). Complexes 1 and 2 were structurally characterized by X-ray crystallography (Figure 2).…”

Section: ■ Results and Discussionmentioning

confidence: 85%

“…The Fe(2)−C(7) (2.1512(18) Å for 1, 2.186(3) Å for 2) distances are similar to those of diiron complexes derived from benzothiophene (2.197(4) Å) 38 and QTs (ca. 2.14 Å) 33 rather than from PyDBT derivatives (2.33−2.36 Å), 36,37 indicating the vinyl group is more tightly bound to Fe through π coordination compared with the central phenyl group in PyBPT derivatives.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“…The yields of 1 and 2 are higher than those of the corresponding photoreactions with PyDBT or QTs. 33,36 The reactivity difference between QBT and PyDBT is probably related to that between benzothiophene and dibenzothiophene for C−S scission (benzothiophene > dibenzothiophene). 38 Moreover, the better π-coordination ability of the vinyl moiety stabilizes the dinuclear structure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

et al. 2020

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Iron(III) carbonyl complexes of N,C,S-tridentate ligands containing quinoline-N, vinyl-C, and benzenethiolate-S donors were synthesized by three steps from quinolyl-substituted benzothiophenes via C–S bond cleavage, and their photoreactivity was investigated. The starting complexes [Fe2(μ-L)(CO)5] (L = qvbt and qvbt-OMe) were synthesized by the photoreactions of the ligand precursors with [Fe(CO)5], where qvbt and qvbt-OMe are a doubly deprotonated form of 2-[2-(quinolin-8-yl)vinyl]benzenethiol and its methoxy derivative, respectively. The methoxy group is bound to the vinyl moiety of the ligand, which is the β-position to Fe in the C,S-chelate. The N,C,S-pincer iron(II) carbonyl complexes trans-[Fe(L)(CO)(PMe3)2] were obtained by treatment of [Fe2(μ-L)(CO)5] with PMe3. One-electron oxidation of the iron(II) complexes afforded the N,C,S-pincer iron(III) carbonyl complexes trans-[Fe(L)(CO)(PMe3)2]PF6. The iron(III) carbonyl complex of qvbt was adequately stable in both the solid and solution state, whereas the qvbt-OMe complex underwent thermal decomposition in solution. The instability is related to the steric demand of the methoxy group in the coordinated ligand. Both iron(III) complexes showed the CO-releasing properties induced by visible light in dichloromethane, which is enhanced by the methoxy group on the vinyl moiety.

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Section: ■ Results and Discussionmentioning

confidence: 59%

Section: ■ Results and Discussionmentioning

confidence: 85%

Section: ■ Results and Discussionmentioning

confidence: 96%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

et al. 2020

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“…The DBT-NN complex [Fe 2 (μ-DBT-NN)(CO) 6 ] (1) has π coordination of the Schiff base CvN bond and an N,N-chelate, while the BPT-NN complex [{Fe(μ-BPT-NN-κ 3 S,C,N)(CO) 2 }Fe(CO) 3 ] (2) has an S,C,N-tridentate ligand without an N,N-chelate. This contrasts with the reaction of 6-(4″-dibenzothienyl)-2,2′-bipyridine with [Fe(CO) 5 ], which gives a diiron complex of an S,C,N,N-tetradentate ligand 29. The π coordination of the CvN bond in 1, which is assisted by the N,N-chelate, prevents the access of the C-S bond to Fe.…”

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confidence: 95%

Formation, reactivity and redox properties of carbon- and sulfur-bridged diiron complexes derived from dibenzothienyl Schiff bases: effect of N,N- and N,P-chelating moieties

2015

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Dibenzothienyl Schiff bases, DBT-NN and DBT-NP, were derived from condensation of 4-formyldibenzothiophene with N,N-dimethylethylenediamine and 2-(diphenylphosphino)ethylamine, respectively. A photochemical reaction of [Fe(CO)5] with DBT-NN produced diiron complexes, [Fe2(μ-DBT-NN)(CO)6] (1) and [{Fe(μ-BPT-NN-κ(3)S,C,N)(CO)2}Fe(CO)3] (2). Complex 1 has π coordination of a Schiff base C=N bond and an N,N-chelate, while 2 has an S,C,N-tridentate ligand having an uncoordinated dimethylamino group. The corresponding reaction with DBT-NP produced a diiron complex of an S,C,N,P-tetradentate ligand, [{Fe(μ-BPT-NP-κ(4)S,C,N,P)(CO)}Fe(CO)3] (3), which has an N,P-chelate, via the DBT-NP complex [Fe(DBT-NP-κP)(CO)4] (4). Reactions of 2 and 3 with one equivalent of PMe2Ph gave the monosubstituted complexes [{Fe(μ-BPT-NN-κ(3)S,C,N)(CO)2}Fe(CO)2(PMe2Ph)] (5) and [{Fe(μ-BPT-NP-κ(4)S,C,N,P)(CO)}Fe(CO)2(PMe2Ph)] (6), respectively. The corresponding reactions with an excess of PMe2Ph produced mononuclear complexes, trans-[Fe(BPT-NN-κ(3)S,C,N)(CO)(PMe2Ph)2] (7) and [Fe(BPT-NP-κ(4)S,C,N,P)(CO)(PMe2Ph)] (8), respectively. Complexes 1-3 and 5-8 were structurally characterized by X-ray crystallography. Complexes 2, 3, 5 and 6 have similar dinuclear structures with different carbonyl/phosphine substitution patterns. Cyclic voltammograms of 2, 3 and 5 showed two one-electron reduction processes, and more negative potentials were observed for 6. The shift of the redox potentials are rationalized by the electron-donating character of the phosphine ligands, which suggests that the reduction occurs at the asymmetrically bridged diiron core.

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The Chemistry of Metal Thiophenolates

Klingele¹,

Kersting²

2013

Patai's Chemistry of Functional Groups

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The present article reviews structures, properties, reactivity and applications of transition metal complexes supported by the parent thiophenolate ligand system and various derivatives thereof. This extensive outline of literature published in the last decade covers publications about di‐ and higher nuclear complexes that exhibit bridging thiophenolate functions. The structuring of this contribution is based on the type of ligand involved in the coordination, covering monodentate thiophenolate ligands as well as bi‐ and higher dentate derivatives being acyclic or macrocyclic. An emphasis is set on structures but reactions, reactivity and catalysis, redox chemistry, and other properties of the complexes in review are discussed where appropriate.

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Carbon–sulfur bond cleavage reactions of dibenzothiophene derivatives mediated by iron and ruthenium carbonyls

Cited by 30 publications

References 17 publications

Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

Formation, reactivity and redox properties of carbon- and sulfur-bridged diiron complexes derived from dibenzothienyl Schiff bases: effect of N,N- and N,P-chelating moieties

The Chemistry of Metal Thiophenolates

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