Synthesis and Characterization of a Metallapyridyne Complex

Wang, Tongdao; Zhang, Hong; Han, Feifei; Lin, Ran; Lin, Zhenyang; Xia, Haiping

doi:10.1002/anie.201204073

Cited by 73 publications

(46 citation statements)

References 65 publications

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“…The Os1=N1 bond length (1.806(10) Å) is within the typical range of bond lengths for azavinylidene–osmium complexes (1.777–1.881 Å),–– and the N1=C4 bond length (1.261(15) Å) is in the expected range for C=N double‐bond lengths. The Os1−C1 (2.095(11) Å) and C1=C2 (1.350(16) Å) bond lengths are similar to those found in other osmium–vinyl metallacycles and support the presence of a vinyl moiety. In contrast to the metallacycles in 2 a and 3 a , that in complex 4 a clearly deviates from planarity, which is reflected by the sum of the angles in the six‐membered ring (713.4°).…”

Section: Resultssupporting

confidence: 73%

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: 73%

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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“…采用这种方法, 不仅可以合成具有高度热稳定性的金属杂苯 [8] , 还可以稳定经典有机中多种重要的活性中间体, 如异苯 [9] 、苯炔 [10] 和吡啶炔 [11] . 这些金属杂环化合物在空气氛中均具有较高的热稳定性.…”

Section: 高活性物种(如: 环内累积多烯、芳炔等)是有机反应的重要中间体unclassified

“…虽然目前有多例金属苯炔化合物的合成报道, 但是, 金属吡啶炔一直未见报道. 我们课题组 [11] 发现在引入金属的同时, 在主环上引入季鏻取代基, 可以有效地稳定吡啶炔化合物(Chart 5). 有趣的是, 在化合物 12 和 13 中, 氮原子均位于金属的间位(Chart 6, B).…”

Section: 金属吡啶炔unclassified

Double Stabilization of Highly Strained Six-Membered Rings by Phosphonium and Transition Metal

Zhu¹,

Zou²,

Xia³

2013

Chin. J. Org. Chem.

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Cycloalkynes and cyclocumulenes have attracted considerable attention because they are key intermediates in organic synthesis. Stabilization of these highly active species remains a challenge for synthetic chemists. Recently, we found that phosphonium and transition metal replacement can double stabilize these species. Using this strategy, a series of highly strained six-membered rings with remarkable stability have been synthesized. Herein, the latest progress of our group is reviewed.

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“…Although the isolation and study of a considerable number of metallabenzenes and fused‐ring metallabenzenes has been reported, much remains to be explored regarding the reactivity of these compounds. Studies carried out so far have demonstrated that the transition metal modifies significantly the delocalized π‐system and the chemical reactivity compared to the corresponding organic analogues . Theoretical studies have shown that the nature and position of ring substituents can have a large influence on the stability and reactivity of metallabenzenes …”

Section: Introductionmentioning

confidence: 99%

Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

Frogley

Perera

Wright

2017

Chemistry A European J

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The first examples of amino-substituted fused-ring metallabenzenes, the cationic iridabenzofuran [Ir(C H O{NH -2}{OMe-7})(CO)(PPh ) ][O SCF ] (5) and neutral analogue Ir(C H {NH -2}{OMe-7})Cl(PPh ) (6), can be prepared by reduction of the corresponding nitro-substituted iridabenzofurans with zinc and concentrated hydrochloric acid. N-functionalised derivatives of 5 and 6 are formed through alkylation, sulfonylation or acylation. Thus, consecutive treatments with methyl triflate and base gives the corresponding trimethylammonium-substituted iridabenzofurans while sulfonamide derivatives are formed with p-toluenesulfonyl chloride. N-Acylation of 5 or 6 with acid chlorides, however, selectively form either amide or imide products depending on the charge on the metal and the steric size of the acid chloride. Cationic 5 gives amide substituted products regardless of the conditions whereas neutral 6 rapidly undergoes di-N-acylation with excess benzoyl chloride under mild conditions to give the imide-substituted product Ir(C H O{N[C(O)Ph] -2}{OMe-7})Cl(PPh ) (13). Selective mono-acylation of 6 can be achieved with one equivalent of benzoyl chloride or with excess of the sterically congested pivaloyl chloride.

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Synthesis and Characterization of a Metallapyridyne Complex

Cited by 73 publications

References 65 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

Double Stabilization of Highly Strained Six-Membered Rings by Phosphonium and Transition Metal

Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

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