Metallafurans and their synthetic chemistry

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Metalla-aromatics are attractive species because they exhibit the properties of both organometallics and aromatics. Reported metal-bridged polycyclic aromatic complexes, as well as Möbius aromatic species, are still rare. Herein, we present the construction of two new metal-bridged polycyclic aromatic frameworks, α-metallapentalenofurans and lactone-fused metallapentalynes, by the reactions of osmapentalyne with terminal aryl alkynes in the presence of H O or HBF /H O, respectively. DFT calculations show that the α-metallapentalenofurans possess rare planar Craig-type Möbius aromaticity derived from the 11-center-12-electron d -p π-conjugation. This study offers a new route for the construction of polycyclic metalla-aromatics as well as planar Möbius aromatic species.

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Metallapentalenofurans and Lactone‐Fused Metallapentalynes

Lü

Zhu

Cai

et al. 2017

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“…[18] However,t he chemistry of b-metallapentalenofurans (8)h as still been under studied. [19] In this work, we reportt he reverse of reductive elimination and oxidative addition between b-metallapentalenofurans and metallapentalynes, whiche nriches the reactivity of carbolong complexes. The reaction mechanism was also studied with the helpofDFT calculations.…”

Section: Introductionmentioning

confidence: 87%

“…X-ray molecular structure of the cation of complex 11 drawn at the 50 %p robability level. Phenylgroups in PPh 3 moieties were omitted for clarity.S electedb ond lengths[ ]and angles[ 8]: OsÀC1:2.085(5), Os1ÀC4: 2.072(5), Os1ÀC7:2 .023(5), Os1ÀC8:1.987(5), C1ÀC2:1.382(7), C2ÀC3: 1.431(7), C3ÀC4:1 .381(7), C4ÀC5:1.422(7), C5ÀC6:1 .375(6), C6ÀC7:1.454 (6); Os1-C1-C2: 115.9(4), C1-C2-C3:1 16.4(4), C2-C3-C4:1 12.5(4),C 3-C4-Os1: 118.6(3), C4-Os1-C1:76.6 (19), Os1-C4-C5: 115.6(3), C4-C5-C6:1 14.9(4),C 5-C6-C7:1 14.2(4), C6-C7-Os1:1 15.9(3),C 7-Os1-C4:7 7.9 (19), P1-Os1-P2:167.8 (5).…”

Section: Shiftable Metallafuran Ringsmentioning

confidence: 99%

“…[20] When D 2 Ow as used in this phosphonium-eliminated reaction, the deuterium-labeled complex 13D was isolated and its structure was supportedb y (3), C1ÀC2:1 .401(4),C2 ÀC3: 1.408(4), C3ÀC4:1 .388(4), C4ÀC5:1.400(4), C5ÀC6:1 .381(4), C6ÀC7:1.415(4), C10ÀC11: 1.395(4), C11ÀO2:1 .385(4), C1ÀO2:1 .350 (3);Os1-C1-C2:1 20.9(2), C1-C2-C3:1 11.5(3), C2-C3-C4: 115.2(4), C3-C4-Os1:1 17.9(2), C4-Os1-C1: 74.52 (12), Os1-C4-C5:1 18.1(2), C4-C5-C6: 114.8 (3), C5-C6-C7:1 13.1(3), C6-C7-Os1:1 18.6(2), C7-Os1-C4:7 4.38 (12), Os1-10-C11: 114.2(2), C10-C11-O2: 117.1(3), C11-O2-C1:1 12.3(2), O2-C1-Os1:1 22.2(2),C 1-Os1-C10:7 4.0(11), P1-Os1-P2:175.69 (2). (4), Os1-C1-C2:1 19.83 (19), C1-C2-C3:1 12.9(3), C2-C3-C4: 115.0(2), C3-C4-Os1: 118.14 (19), C4-Os1-C1: 73.91(10), Os1-C4-C5:1 17.8 (2), C4-C5-C6:1 15.8 (2), C5-C6-C7: 111.5 (2), C6-C7-Os1: 120.6(2), C7-Os1-C4: 74.31(10), Os1-C10-C11: 114.73 (19), C10-C11-O1: 117.2(2), C11-O1-C7:1 11.8(2), O1-C7-Os1:1 22.12(18), C7-Os1-C10:73.99(10), P1-Os1-P2:174.51 (2). dicatedt hat the proton attached at C2 was originated from water.…”

Section: Shiftable Metallafuran Ringsmentioning

confidence: 99%

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Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects

Hua

Lan

Fei

et al. 2018

Self Cite

Bulky substituents play important roles in controlling the reaction pathways or producing selected products. This work reports that the shift of metallafuran rings in a metallapentalenofuran complex can be promoted by the substituent effect via a reversible C-H bond reductive elimination and oxidative addition. The starting osmapentalyne, a so-called 7-carbon carbolong complex, was produced by the oxidation of a metallapentalenofuran with FeCl . It was then allowed to react with nucleophiles, followed by a C-H activation, to give the aforementioned metallapentalenofuran complex. This work enriches the family of carbolong complexes and reveals a new strategy to promote, but not prevent reactions by the bulky substituents.

Synthesis and Characterization of Photothermal Osmium Carbolong Complexes

Qin

Lin

et al. 2018

Self Cite

Metallacycles with chelating polydentate conjugated-carbon chain ligands are called carbolong complexes, which are expected to have interesting properties. In this work, the preparation of 12-carbon carbolong complexes in which all of the coordinated atoms in the equatorial plane are carbon atoms was studied. With the help of the well-established mechanism, a new approach to prepare coplanar carbolong complexes bearing different organic functional groups was developed by adding different terminal alkynes in sequence. In the presence of HBF , these coplanar carbolong complexes were converted to η -allyl osmapentalene derivatives, which can be produced directly from the reaction of cyclopropaosmapentalene 1 with terminal alkynes in the presence of AgBF under anhydrous conditions. This study offers a new route for the preparation of functional osmium carbolong complexes with excellent photothermal properties, which can be used to prepare photothermal materials.