Synthesis of Five‐Membered Osmacycloallenes and Conversion into Six‐Membered Osmacycloallenes

Wang, Tongdao; Zhu, Jun; Han, Feifei; Zhou, Chen; Chen, Hanyu; Zhang, Hong; Xia, Haiping

doi:10.1002/anie.201306911

Cited by 23 publications

(27 citation statements)

References 61 publications

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“…Furthermore, in the case of model complex 4’ , the strain energy was calculated to be 3.1 kcal mol −1 . These DFT results agree well with previous reports, which showed that introduction of a transition‐metal atom or a main‐group heteroatom is an efficient strategy to reduce the inherent ring strain in cycloallenes …”

Section: Resultssupporting

confidence: 92%

“…The structurald ata indicate that 3a is the first iso-metallapyridinium with form IV (Scheme 1), which is closely related to the iso-metallabenzenes.I ti sw orth noting that the Os1-C1-C2 angle (150.5(6)8)d eviates considerably from linearity and is even smaller than those of reported six-membered iso-metallabenzenes (155.1 (8)8 [5b] and 158.5(3)8 [5c] and iso-metallabenzenones (152.7(5)8 and 151.1(2)8). [6] This is further support that resonance form 3A is an important contribution to the overall structure of complex 3a.…”

Section: Resultsmentioning

confidence: 99%

“…Av iew of the complex cation is shown in Figure 3. The X-ray indicates that 4a (2) 173 (2) 173 (2) 173 (2) (17) 84.2(2) Os1-C1-C21 28.6(8)1 50.5 (6) 128.8(9)1 30.7(3)1 33.1(5) C1-C2-C3 125.8 (10) 115.2 (6) 127.2 (10) 127.0(4)1 23.5(6) C2-C3-C4 118.1(10) 114.7 (6) 109.0(9)1 11.5(4) 112.9(6) C3-C4-N1 121.0(11) 124.3 (7) 116.7 (10) 119.0(4) 123.5(6) C4-N1-Os1 139.4(9) 135.1(5) 152.5(8)1 52.9(3)1 34.8(5) Figure 2. Molecular structure of 3a.The hydrogen atoms of PPh 3 are omitted for clarity.…”

Section: Resultsmentioning

confidence: 99%

“…[5b, c] We have recently verifiedt he existence of the first five-membered metallacycles that contain am etal-vinylidene moiety (III)a nd the conversion of these compounds to their analogous six-membered metallacycles (II). [6] So far,r eported examples of cyclic vinylidene-metal complexes are limited to these three types.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Chen

Huang

Lü

et al. 2016

Chemistry A European J

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Reactions of the hydrido-butenylcarbyne complex [OsHCl2(≡CC(PPh3)=CHEt)(PPh3)2]BF4 (1) with nitriles RC≡N (R=2-cyclopropyl-2-oxopropyl, 3-amino-2-oxobutyl) lead to six-membered cyclic vinylidene complexes 3 and azavinylidene complexes 4, that is, iso-osmapyridiniums. Treatment of 1 with excess 2-formylbenzonitrile at reflux temperature in CHCl3 in the presence of air produces a fused osmapyridinium 8, which is first oxidized to the tricyclic iso-osmapyridinium derivative 7, then to iso-osmapyridinium 9, which contains a fused naphthalenone fragment. The conversion of iso-osmapyridinium 9 (with a vinylidene segment) to the iso-osmapyridinium compounds 10 and 11 (with azavinylidene segments) was achieved in the presence of a hydrogen halide, such as HCl or HI. The molecular structures of the complexes synthesized were confirmed by X-ray studies. Moreover, the aromatic stabilization energy and nucleus-independent chemical-shift values of the osmapyridiniums and the strain in the iso-osmapyridinium rings were investigated by DFT calculations.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Chen

Huang

Lü

et al. 2016

Chemistry A European J

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“…The structures with CCC unit in five‐membered metallacycles, e.g., metallacycloallenes12 and metallacyclocumulenes,13 have been reported experimentally and theoretically. In contrast, the similar structure with a MCC unit in a five‐membered ring has only one example reported by us recently 14…”

Section: Methodsmentioning

confidence: 82%

Five‐Membered Cyclic Metal Carbyne: Synthesis of Osmapentalynes by the Reactions of Osmapentalene with Allene, Alkyne, and Alkene

Zhu

Yang

et al. 2015

Angewandte Chemie

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The synthesis of small cyclic metal carbynes is challenging due to the large angle strain associated with the highly distorted nonlinear triple bonds. Herein, we report a general route for the synthesis of five‐membered cyclic metal carbyne complexes, osmapentalynes, by the reactions of an osmapentalene derivative with allene, alkyne, and alkene. Experimental observations and theoretical calculations document the aromaticity in the fused five‐membered rings of osmapentalynes. The realization of transforming osmapentalene to osmapentalyne through this general route would not only allow further exploration of metallapentalyne chemistry but also show promising applications of this novel aromatic system with broad absorption band and high molar absorption coefficient.

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Haiping Xia

2014

Angewandte Chemie

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Synthesis of Five‐Membered Osmacycloallenes and Conversion into Six‐Membered Osmacycloallenes

Abstract: Details of the preparation and characterization of 4 and 5 can be found in the Supporting Information.

Cited by 23 publications

References 61 publications

Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Five‐Membered Cyclic Metal Carbyne: Synthesis of Osmapentalynes by the Reactions of Osmapentalene with Allene, Alkyne, and Alkene

Haiping Xia

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