Recent development in the chemistry of transition metal-containing metallabenzenes and metallabenzynes

Chen, Jiangxi; Jia, Guochen

doi:10.1016/j.ccr.2013.01.014

Cited by 191 publications

(104 citation statements)

References 153 publications

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“…2, in which Os1 À C4 is always a single s-bond, similar to the previous observation in osmapentalynes 19 . Distances of C À C bonds (1.365-1.414 Å) of the fused five-membered rings are between C À C single-and double-bond lengths, indicating a delocalized structure [33][34][35][36][37][38][39][40][41][42] . Complex 3-(BF 4 ) 2 was further characterized by 1 H, 31 P and 13 C NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

et al. 2014

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Aromaticity, a highly stabilizing feature of molecules with delocalized electrons in closed circuits, is generally restricted to 'Hückel' systems with 4n þ 2 mobile electrons. Although the Möbius concept extends the principle of aromaticity to 4n mobile electron species, the rare known examples have complex, twisted topologies whose extension is unlikely. Here we report the realization of osmapentalenes, the first planar Möbius aromatic complexes with 16 and 18 valence electron transition metals. The Möbius aromaticity of these osmapentalenes, documented by X-ray structural, magnetic and theoretical analyses, demonstrates the basis of the aromaticity of the parent osmapentalynes. All these osmapentalenes are formed by both electrophilic and nucleophilic reactions of the in-plane p component of the same carbyne carbon, illustrating ambiphilic carbyne reactivity, which is seldom observed in transition metal chemistry. Our results widen the scope of Möbius aromaticity dramatically and open prospects for the generalization of planar Möbius aromatic chemistry.

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Section: Resultsmentioning

confidence: 99%

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

et al. 2014

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“…Recently reported examples include metallabenzynes, metallapentalynes, and metallapentalenes . While metallabenzenes (Scheme ) are the best known of these compounds, fused‐ring metallabenzenes are relatively rare and have been much less studied . Fused‐ring metallabenzenes can be divided into two broad categories: 1) those in which the fused ring can in principle support a delocalized π‐bonding system ((A), Scheme , e.g.…”

Section: Methodsmentioning

confidence: 99%

A Metallaanthracene and Derived Metallaanthraquinone

Frogley

Wright

2016

Angewandte Chemie

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Metalla‐analogues of archetypal aromatic molecules are attracting ever increasing interest. Although metallabenzenes (which fall within this class) have been well studied, fused‐ring metallabenzenes are rare and of the linear polycyclic metallaaromatic hydrocarbons, only metallanaphthalene is known. Herein we report the first metallaanthracene, [Ir(C13H8{CH2CO2Me‐5})Cl(PPh3)2]O3SCF3 (5), which represents the next member of this series of polycyclic compounds. Structurally, 5 has a number of features in common with anthracene including fused‐ring planarity and bond‐length alternation. In analogues of classic reactions of anthracene, 5 forms a Diels–Alder adduct with maleic anhydride and on oxidation the unprecedented fused‐ring metallaanthraquinone, [Ir(C15H6O{Br‐6}{OMe‐7}{=O‐8}{=O‐15})Br(PPh3)2], is obtained.

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“…For C 5 rings, this alternative is often, but not always, less thermodynamically stable than forming a complex. 25,26 There are welldocumented cases wherein cyclo-MC 5 R 5 complexes (I) isomerize to ( 5 -C 5 R 5 )M (I=). 27 When it comes to unsaturated thiazyl (-S=N-) ring compounds, the evidence amassed thus far is that insertion (by oxidative addition) dominates.…”

Section: Introductionmentioning

confidence: 99%

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

et al. 2015

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Coordination complexes of thiazyl rings -Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO) x (x = 2, 3) complexes of fluorinated and nonfluorinated 1 3 -1,2,4,6-thiatriazinyls with differing Cr-S bond orders Abstract: The reaction of [3,5-Ph 2 -C 2 N 3 S] 2 with [CpCr(CO) 3 ] 2 in toluene at room temperature forms an adduct via a Cr-S bond, formulated as CpCr(CO) 3 SN 3 C 2 Ph 2 , which has fitting NMR, IR, and combustion analysis data. The structure was determined by a single-crystal X-ray structure diffraction study (P2 1 /n, a = 8.4611(17) Å, b = 20.509(4) Å, c = 11.757(2) Å, ␤ = 104.453(7)°). The Cr-S bond length of 2.4908(11) Å corresponds to a bond order of 1.0 from >90 values for CpCr(CO) x or Cp*Cr(CO) x moieties (x = 2, 3) bonded to S, which are used to establish a Pauling-type bond order scale specific to this class of compounds. Similar reactions of fluorinated thiatriazinyls derived from [3-Ph-5-CF 3 -C 2 N 3 S] 2 or [4-MeOC 6 H 4 -5-CF 3 -C 2 N 3 S] 2 are accompanied by the loss of CO to produce CpCr(CO) 2 SN 3 C 2 PhCF 3 (P1, a = 8.0929(8) Å, b = 10.3160(10) Å, c = 11.2405(11) Å, ␣ = 70.032(2)°, ␤ = 72.076(2)°, ␥ = 82.375(2)°) and CpCr(CO) 2 SN 3 (CCF 3 )(C 6 H 4 OCH 3 ) (P2 1 /c, a = 8.1311(7) Å, b = 24.284(2) Å, c = 9.1025(8) Å, ␤ = 97.218(2)°), also fully characterized by spectroscopy and crystallography. Their measured Cr-S bond lengths, 2.2987(14) and 2.2965(11) Å, correspond to bond orders of 1.5. (U/R)B3PW91/6-311+G(2df,2p)//B3PW91/6-31G(2d,p) hybrid density functional theory (DFT) calculations show that the tricarbonyl complex has an unusual bond. However, the dicarbonyl complexes of the fluorinated thiatriazinyls are bonded.

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Recent development in the chemistry of transition metal-containing metallabenzenes and metallabenzynes

Cited by 191 publications

References 153 publications

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

A Metallaanthracene and Derived Metallaanthraquinone

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

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Recent development in the chemistry of transition metal-containing metallabenzenes and metallabenzynes

Cited by 191 publications

References 153 publications

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums

A Metallaanthracene and Derived Metallaanthraquinone

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ3-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

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Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders